U.S. patent number 7,208,559 [Application Number 10/539,038] was granted by the patent office on 2007-04-24 for ethylened polymer and molded object obtained therefrom.
This patent grant is currently assigned to Mitsui Chemicals, Inc.. Invention is credited to Hideki Bando, Yasushi Nakayama, Yasuo Satoh, Yoshiho Sonobe, Mamoru Takahashi.
United States Patent |
7,208,559 |
Satoh , et al. |
April 24, 2007 |
Ethylened polymer and molded object obtained therefrom
Abstract
An ethylene-based polymer which is an ethylene/C4 to C10
.alpha.-olefin copolymer and satisfies the following requirements
[k1] to [k3]: [k1] melt flow rate (MFR) under a loading of 2.16 kg
at 190.degree. C. is in the range of 1.0 to 50 g/10 minutes; [k2]
LNR defined as a scale of neck-in upon film molding is in the range
of 0.6 to 1.4; and [k3] take-up speed at break [DS (m/min)] at
160.degree. C. and melt flow rate (MFR) satisfy the following
relationship (Eq-1):
12.times.MFR.sup.0.577.ltoreq.DS.ltoreq.165.times.MFR.sup.0.577
(Eq-1), and a thermoplastic resin composition containing the
ethylene-based polymer, provide a molded product, preferably a
film, excellent in moldability and mechanical strength. The
ethylene-based polymer can be efficiently obtained by
polymerization in the presence of an olefin polymerization catalyst
formed from a solid carrier, (A) a solid transition metal catalyst
component obtained by contacting (a) a compound of a transition
metal of the group 4 in the periodic table, containing at least one
ligand having a cyclopentadienyl skeleton, (b) an organoaluminum
oxy compound, (c) a multifunctional organic halide, and if
necessary (d) an organoaluminum compound, and if necessary (B)
organoaluminum compound.
Inventors: |
Satoh; Yasuo (Sodegaura,
JP), Takahashi; Mamoru (Sodegaura, JP),
Bando; Hideki (Sodegaura, JP), Sonobe; Yoshiho
(Sodegaura, JP), Nakayama; Yasushi (Sodegaura,
JP) |
Assignee: |
Mitsui Chemicals, Inc. (Tokyo,
JP)
|
Family
ID: |
32716328 |
Appl.
No.: |
10/539,038 |
Filed: |
December 15, 2003 |
PCT
Filed: |
December 15, 2003 |
PCT No.: |
PCT/JP03/16660 |
371(c)(1),(2),(4) Date: |
June 15, 2005 |
PCT
Pub. No.: |
WO2004/060932 |
PCT
Pub. Date: |
July 22, 2004 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20060135712 A1 |
Jun 22, 2006 |
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Foreign Application Priority Data
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Dec 27, 2002 [JP] |
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2002-381141 |
Dec 27, 2002 [JP] |
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2002-381142 |
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Current U.S.
Class: |
526/348.6;
502/125; 502/124; 502/129; 526/142; 526/147; 526/170; 526/348;
526/348.2; 526/348.3; 526/348.5; 526/352.2; 528/396; 526/160;
526/141; 502/123; 526/143 |
Current CPC
Class: |
C08F
10/00 (20130101); C08F 10/00 (20130101); C08F
4/65912 (20130101); C08F 4/65927 (20130101); C08F
4/65916 (20130101) |
Current International
Class: |
C08F
10/08 (20060101); C08F 10/02 (20060101) |
Field of
Search: |
;528/396
;526/348,160,170,143,141,147,348.6,348.2,348.5,348.3,142
;502/129,125,123,124 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0 452 920 |
|
Oct 1991 |
|
EP |
|
2-276807 |
|
Nov 1990 |
|
JP |
|
4-213309 |
|
Aug 1992 |
|
JP |
|
6-65443 |
|
Mar 1994 |
|
JP |
|
6-172594 |
|
Jun 1994 |
|
JP |
|
8/34819 |
|
Feb 1996 |
|
JP |
|
8/311260 |
|
Nov 1996 |
|
JP |
|
8-319313 |
|
Dec 1996 |
|
JP |
|
9-249707 |
|
Sep 1997 |
|
JP |
|
11-166083 |
|
Jun 1999 |
|
JP |
|
WO-93/08221 |
|
Apr 1993 |
|
WO |
|
Primary Examiner: Choi; Ling-Sui
Assistant Examiner: Lee; Rip A.
Attorney, Agent or Firm: Birch, Stewart, Kolasch &
Birch, LLP
Claims
The invention claimed is:
1. An ethylene-based polymer which is an ethylene/C4 to C10
.alpha.-olefin copolymer and satisfies the following requirements
[k1] to [k3] simultaneously: [k1] melt flow rate (MFR) under a
loading of 2.16 kg at 190.degree. C. is in the range of 1.0 to 50
g/10 minutes; [k2] LNR defined as a scale of neck-in upon film
molding is in the range of 0.6 to 1.4; and [k3] take-up speed at
break [DS (m/min)] at 160.degree. C. and melt flow rate (MFR)
satisfy the following relationship (Eq-1):
12.times.MFR.sup.0.577.ltoreq.DS.ltoreq.165.times.MFR.sup.0577
(Eq-1).
2. The ethylene-based polymer according to claim 1, which
simultaneously satisfies the following requirements [m1] to [m3]:
[m1] density [d] is in the range of 890 to 950 kg/m.sup.3; [m2]
ratio [MT/.eta.* (g/Poise)] of melt tension [MT (g)] at 190.degree.
C. to shearing viscosity [.eta.* (Poise)] at 200.degree. C. at an
angular velocity of 1.0 rad/sec. is in the range of
2.00.times.10.sup.-4 to 9.00.times.10.sup.-4; and [m3] sum
[(A+B)(/1000C)] of the number of methyl branches [A (/1000C)] and
the number of ethyl branches [B (/1000C)] per 1000 carbon atoms
measured by .sup.3C-NMR is 1.4 or less.
3. The ethylene-based polymer according to claim 1 or 2, which
satisfies at least one of the following requirements [n1] to [n3]:
[n1] ratio (Mz/Mw) of Z-average molecular weight (Mz) to
weight-average molecular weight (Mw), measured by GPC, is 10 or
more; [n2] the number of terminal vinyl groups (V) per molecular
chain is not higher than 0.47 per molecular chain and is calculated
from the number of terminal vinyl groups [v (/1000C)] per 1000
carbon atoms measured by IR and number-average molecular weight
(Mn) measured by GPC; or [n3] melting-point maximum peak [Tm
(.degree. C.)] in DSC and density (d) satisfy the following
relationship (Eq-2):
(0.315.times.d)-200.ltoreq.Tm.ltoreq.(0.315.times.d)-170
(Eq-2).
4. The ethylene-based polymer according to claim 1, which is
obtained by polymerization using an olefin polymerization catalyst
formed from: a solid carrier, and (A) a solid transition metal
catalyst component obtained by contacting: (a) a compound of a
transition metal of the group 4 in the periodic table, containing
at least one ligand having a cyclopentadienyl skeleton, (b) an
organoaluminum oxy compound, and (c) a multifunctional organic
halide represented by the following general formula (I):
(Q.sup.1).sub.o--R--(Q.sup.2).sub.p (I) wherein R is a (o+p)-valent
group containing at least one halogen atom, o and p each represent
a positive integer satisfying the relationship (o+p).gtoreq.2,
Q.sup.1 and Q.sup.2 each represent --OH, --NH.sub.2 or --NLH
whereupon L is an arbitrary group selected from a C1 to C20
hydrocarbon group, a C1 to C20 halogen-containing hydrocarbon
group, a silicon-containing group, an oxygen-containing group, a
sulfur-containing group, a nitrogen-containing group or a
phosphorus-containing group, and L and R, N and R, or N and N may
be bound to each other to form a ring, and if necessary (d) an
organoaluminum compound, and if necessary (B) an organoaluminum
compound.
5. The ethylene-based polymer according to claim 4, which is
obtained by polymerization in the presence of a catalyst formed
from: a preliminary polymer having a z-average molecular weight of
6,000,000 or more by GPC and having a die-swell ratio of 1.4 or
more, pre-polymerized by ethylene, or ethylene and a C4 to C10
.alpha.-olefin, with the solid transition metal catalyst component,
wherein 0.01 to 1000 g of the polymer is contained per g of the
solid transition metal catalyst component, and if necessary (B) an
organoaluminum compound.
6. The ethylene-based polymer according to claim 4, wherein the
compound (a) of a transition metal of the group 4 in the periodic
table, containing at least one ligand having a cyclopentadienyl
skeleton, is a compound represented by the following general
formula (II), (III) or (IV): ##STR00005## wherein R.sup.1 to
R.sup.6 are independently selected from a hydrogen atom, a halogen
atom, a C1 to C20 alkyl group, a C3 to C20 cycloalkyl group, a C2
to C20 alkenyl group, a C6 to C20 aryl group, and a C7 to C20
arylalkyl group, respectively, or can contain a silicon, halogen or
germanium atom, and at least one pair of R.sup.3 and R.sup.4,
R.sup.4 and R.sup.5, and R.sup.5 and R.sup.6 may be bound to each
other to form a ring, R.sup.7 is a divalent group having two
ligands, and is a C1 to C20 hydrocarbon group, a C1 to C20
halogen-containing hydrocarbon group, a silicon-containing group or
a germanium- or tin-containing group, and two substituent groups on
the same carbon, silicon, germanium or tin atom may be bound to
each other to form a ring, t.sup.1 and t.sup.2 independently
represent a group selected from a hydrogen atom, a halogen atom, a
C1 to C20 hydrocarbon group, a C1 to C20 halogen-containing
hydrocarbon group, a silicon-containing group, an oxygen-containing
group, a sulfur-containing group, a nitrogen-containing group or a
phosphorus-containing group, respectively, and M is a transition
metal selected from titanium, zirconium or hafnium, ##STR00006##
wherein R.sup.7, t.sup.1, t.sup.2 and M each have the same meaning
as defined in formula (II), R.sup.8 to R.sup.19 independently
represent a hydrogen atom, a halogen atom, a C1 to C20 alkyl group,
a C3 to C20 cycloalkyl group, a C2 to C20 alkenyl group, a C6 to
C20 aryl group or a C7 to C20 arylalkyl group, respectively, and
can contain a silicon, halogen or germanium atom, and adjacent
substituent groups out of R.sup.8 to R.sup.9 may be bound to each
other to form a ring.
7. A thermoplastic resin composition comprising the ethylene-based
polymer according to claim 1.
8. A molded product obtained from the ethylene-based polymer
according to claim 1.
9. A molded product obtained from the thermoplastic resin
composition according to claim 7.
10. The molded product according to claim 8 or 9, wherein the
molded product is a film.
Description
TECHNICAL FIELD
The present invention relates to a novel ethylene-based polymer
superior in moldability and mechanical strength to conventionally
known ethylene-based polymers, a thermoplastic resin composition
containing the ethylene-based polymer, and a molded product,
preferably a film, obtained from the ethylene-based polymer and the
thermoplastic resin composition. The present invention also relates
to the ethylene-basedpolymer obtained from a specific olefin
polymerization catalyst.
BACKGROUND ART
Ethylene-based polymers are formed by various molding methods and
subjected to various applications. Characteristics required of the
ethylene-based polymer vary depending on the molding method and
applications. For example, when a cast film is to be formed in
T-die molding, there arises neck-in wherein the edge of the film is
shrunk in a direction toward the center. When neck-in occurs, the
film width is decreased and simultaneously the film edge is thicker
than the film center, thus reducing the product yield. To minimize
neck-in, an ethylene-based polymer having high melt tension
relative to molecular weight should be selected. This property is
also necessary for preventing sagging or rupture in blow molding or
for preventing bubble tremble or rupture in inflation film.
High-pressure low-density polyethylene is used in films and hollow
containers because it is superior in moldability with high melt
tension to an ethylene-based polymer produced using a Ziegler
catalyst. However, the high-pressure low-density polyethylene has a
complicated long-chain branched structure, and is thus expected to
be inferior in mechanical strength such as tensile strength, tear
strength or impact resistance. For the same reason, it is expected
to be inferior in high-speed film processability in T-die
molding.
The ethylene-based polymer obtained by using a metallocene catalyst
among the Ziegler catalysts is excellent in mechanical strength
such as tensile strength, tear strength or impact resistance but is
inferior in melt tension, and is thus expected to exhibit a
deterioration in moldability such as significant neck-in.
As an ethylene-based polymer excellent in moldability and
mechanical strength, a composition comprising high-pressure
low-densitypoly ethylene and an ethylene-based polymer obtained by
using a metallocene catalyst is proposed for example in Japanese
Patent Publication No. H06-65443 etc. However, when the content of
high-pressure low-density polyethylene is low, the composition does
not sufficiently improve melt tension, and is thus expected to
exhibit a deterioration in moldability, such as significant neck-in
in T-die molding. When the content of high-pressure low-density
polyethylene is high, the composition is expected to be inferior in
mechanical strength such as tensile strength, tear strength or
impact resistance.
To solve the problem, various ethylene-based polymers having long
branches introduced into them have been disclosed.
Japanese Patent Publication No. H02-276807 discloses an
ethylene-based polymer obtained by solution polymerization in the
presence of a catalyst consisting of ethylene bis(indenyl) hafnium
dichloride and methyl alumoxane, Japanese Patent Publication No.
H04-213309 discloses an ethylene-based polymer obtained by gaseous
phase polymerization in the presence of a catalyst comprising
ethylene bis(indenyl) zirconium dichloride and methyl alumoxane
carried on silica, WO93/08221 discloses an ethylene-based polymer
obtained by solution polymerization in the presence of a constraint
geometrical catalyst, Japanese Patent Publication No. H08-311260
discloses an ethylene-based polymer obtained by gaseous phase
polymerization in the presence of a catalyst comprising a racemate
and mesoisomer of Me.sub.2Si(2-Me-Ind).sub.2 and methyl alumoxane
carried on silica, Japanese Patent Publication No. H08-34819
discloses an ethylene-based polymer obtained by slurry
polymerization in the presence of a catalyst comprising
bis(cyclopentadienyl) zirconium dichloride carried on chemically
treated montmorilonite, and Japanese Patent Publication No.
H08-319313 discloses an ethylene-based polymer obtained by
polymerization using a catalyst consisting of Cp*Ti (OMe).sub.3 and
methyl alumoxane.
It is described that these ethylene-based polymers, as compared
with long branch-free linear ethylene-based polymers, are excellent
in moldability with improvement in melt tension, but neck-in is
still significant so improvement in moldability is expected to be
insufficient.
To improve moldability, an ethylene-based polymer having a small
amount of a high-molecular component introduced into it is
disclosed.
Japanese Patent Publication No. H06-172594 discloses an
ethylene-based resin composition comprising a high-molecular
component and a low-molecular component, obtained by using a
Ziegler catalyst. This ethylene-based resin composition is expected
to be inferior in moldability because of its too high molecular
weight. Its compositional distribution is expected to be broad
because of use of a Ziegler catalyst that is a multi-site
catalyst.
Japanese Patent Publication No. H11-166083 discloses an
ethylene-based resin composition comprising an ethylene-based
polymer consisting of high- and low-molecular components obtained
by using a Ziegler catalyst and an ethylene-based polymer obtained
by using a Phillips catalyst. This ethylene-based resin composition
is expected to be inferior in low-temperature sealability because
of its too high density. Further the ethylene-based polymer
obtained by using a Phillips catalyst is known to have many
terminal vinyl groups. Accordingly, this ethylene-based resin
composition is inferior in thermal stability. Further, its
compositional distribution is expected to be broad because of use
of a Ziegler catalyst that is a multi-site catalyst.
As described above, resin excellent in moldability and mechanical
strength is hardly efficiently obtained on the basis of the
conventional known techniques. In other words, if an ethylene-based
polymer excellent in moldability and mechanical strength would
appear, its industrial value would be extremely significant.
The present inventors made extensive study in view of these
circumstances, and as a result, they found that an ethylene-based
polymer excellent in high-speed film processability and mechanical
strength with less neck-in in T-die molding is obtained by
conferring a specific molecular structure and melt physical
properties thereon, and the present invention was thereby
completed.
DISCLOSURE OF INVENTION
The object of the present invention is to provide a novel
ethylene-based polymer superior in moldability and mechanical
strength to conventionally known ethylene-based polymers, a
polymerization catalyst for efficiently producing the
ethylene-based polymer, a thermoplastic resin composition
containing the ethylene-based polymer, and a molded product,
preferably a film, obtained from the ethylene-based polymer and the
thermoplastic resin composition.
The ethylene-based polymer of the present invention is an
ethylene/C4 to C10 .alpha.-olefin copolymer satisfying the
following requirements [k1] to [k3]simultaneously: [k1] melt flow
rate (MFR) under a loading of 2.16 kg at 190.degree. C. is in the
range of 1.0 to 50 g/10 minutes; [k2] LNR defined as a scale of
neck-in upon film molding is in the range of 0.6 to 1.4; and [k3]
take-up speed at break [DS (m/min)] at 160.degree. C. and melt flow
rate (MFR) satisfy the following relationship (Eq-1):
12.times.MFR.sup.0.577.ltoreq.DS.ltoreq.165.times.MFR.sup.0.577
(Eq-1)
Preferably, the ethylene-based polymer according to the present
invention simultaneously satisfies the following requirements [m1]
to [m3] in addition to the above requirements: [m1] density [d] is
in the range of 890 to 950 kg/m.sup.3; [m2] ratio [MT/.eta.*
(g/Poise)] of melt tension [MT (g)] at 190.degree. C. to shearing
viscosity [.eta.* (Poise)] at 200.degree. C. at an angular velocity
of 1.0 rad/sec. is in the range of 2.00.times.10.sup.-4 to
9.00.times.10.sup.-4; and [m3] sum [(A+B) (/1000C)] of the number
of methyl branches [A (1000C)] and the number of ethyl branches [B
(/1000C)] measured by .sup.13C-NMR is 1.4 or less.
Preferably, the ethylene-based polymer according to the present
invention simultaneously satisfies any one of the following
requirements [n1] to [n3] in addition to the above requirements:
[n1] ratio (Mz/Mw) of Z-average molecular weight (Mz) to
weight-average molecular weight (Mw), measured by GPC, is 10 or
more; [n2] the number of terminal vinyl groups (V) per molecular
chain calculated from the number of terminal vinyl groups [v
(/1000C)] per 1000 carbon atoms measured by IR and number-average
molecular weight (Mn) measured by GPC is not higher than 0.47 per
molecular chain; and [n3] melting-point maximum peak [Tm (.degree.
C.)] in DSC and density (d) satisfy the following relationship
(Eq-2): 0.315.times.d-200.ltoreq.Tm.ltoreq.0.315.times.d-170
(Eq-2)
The ethylene-based polymer of the present invention can be
efficiently produced by polymerization in the presence of an olefin
polymerization catalyst formed from a solid carrier, (A) a solid
transition metal catalyst component obtained by contacting (a) a
compound of a transition metal of the group 4 in the periodic
table, containing at least one ligand having a cyclopentadienyl
skeleton, (b) an organoaluminum oxy compound, (c) a multifunctional
organic halide represented by the general formula (I), and if
necessary (d) an organoaluminum compound, and if necessary (B)
organoaluminum compound.
The ethylene-based polymer of the present invention can also be
produced efficiently by polymerization in the presence of a
pre-polymerized catalyst formed from a prepolymer having a
z-average molecular weight of 6,000,000 or more by GPC and having a
die-swell ratio of 1.4 or more, obtained by contacting ethylene, or
ethylene and a C4 to C10 .alpha.-olefin, with the solid transition
metal catalyst component, wherein 0.01 to 1000 g of the prepolymer
is contained per g of the solid transition metal catalyst
component, and if necessary (B) an organoaluminum compound.
The multifunctional organic halide (c) is preferably a compound
represented by the following general formula (I):
(Q.sup.1).sub.o--R--(Q.sup.2).sub.p (I) where in R is a
(o+p)-valent group containing at least one halogen atom, o and p
each represent a positive integer satisfying the relationship
(o+p).gtoreq.2, Q.sup.1 and Q.sup.2 each represent --OH, --NH.sub.2
or --NLH whereupon L is an arbitrary group selected from a C1 to
C20 hydrocarbon group, a C1 to C20 halogen-containing hydrocarbon
group, a silicon-containing group, an oxygen-containing group, a
sulfur-containing group, a nitrogen-containing group and a
phosphorus-containing group, and L and R, N and R, or N and N may
be bound to each other to form a ring.
The compound (a) of a transition metal of the group 4 in the
periodic table, containing at least one ligand having a
cyclopentadienyl skeleton, is preferably a compound represented by
the following general formula (II), (III) or (IV):
##STR00001## wherein R.sup.1 to R.sup.6 are independently selected
from a hydrogen atom, a halogen atom, a C1 to C20 alkyl group, a C3
to C20 cycloalkyl group, a C2 to C20 alkenyl group, a C6 to C20
aryl group, and a C7 to C20 arylalkyl group, respectively, and can
contain a silicon, halogen or germanium atom, and at least one pair
of R.sup.3 and R.sup.4, R.sup.4 and R.sup.5, and R5 and R.sup.6 may
be bound to each other to form a ring, R.sup.7 is a divalent group
having two ligands, and is a C1 to C20 hydrocarbon group, a C1 to
C20 halogen-containing hydrocarbon group, a silicon-containing
group or a germanium- or tin-containing group, and two substituent
groups on the same carbon, silicon, germanium or tin atom may be
bound to each other to form a ring, t.sup.1 and
t.sup.2independently represent a group selected from a hydrogen
atom, a halogen atom, a C1 to C20 hydrocarbon group, a C1 to C20
halogen-containing hydrocarbon group, a silicon-containing group,
an oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group and a phosphorus-containing group,
respectively, and M is a transition metal selected from titanium,
zirconium and hafnium,
##STR00002## wherein R.sup.7, t.sup.1, t.sup.2 and M each have the
same meaning as defined in formula (II), R.sup.8 to R.sup.19
independently represent a hydrogen atom, a halogen atom, a C1 to
C20 alkyl group, a C3 to C20 cycloalkyl group, a C2 to C20 alkenyl
group, a C6 to C20 aryl group or a C7 to C20 arylalkyl group,
respectively, and can contain a silicon, halogen or germanium atom,
and adjacent substituent groups out of R.sup.8 to R.sup.19 may be
bound to each other to form a ring.
Further, the ethylene-based polymer according to the present
invention can be blended with another thermoplastic resin to give a
thermoplastic resin composition excellent in moldability and
mechanical strength. The ethylene-based polymer according to the
present invention, and a resin composition containing the
ethylene-based polymer, can be processed to give a molded product,
preferably a film, excellent in moldability and mechanical
strength.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a top view of a slit dice for measuring the neck-in ratio
of a sample according to the present invention.
FIG. 2 is a side view of the slit dice.
FIG. 3 is a sectional view of the slit dice along line A B.
FIG. 4 is a front view of a cooling roll and an air nozzle.
FIG. 5 is a side view of a cooling roll and an air nozzle.
FIG. 6 is a top view of a capillary rheometer for measuring the
die-swell ratio according to the present invention.
FIG. 7 is a side view of the capillary rheometer.
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the best mode for carrying out the invention is
described in more detail by reference to the following 3 parts,
that is, (1) the ethylene-based polymer according to the present
invention, (2) a polymerization catalyst for producing the
ethylene-based polymer, and (3) use of the ethylene-based
polymer.
(1) The Ethylene-Based Polymer According to the Present
Invention
The ethylene-based polymer according to the present invention is a
copolymer of ethylene and a C4 to C10 .alpha.-olefin, preferably
ethylene and a C4 to C10 .alpha.-olefin (provided that when
butene-1 is used as a comonomer, a C6 to C10 .alpha.-olefin shall
also be essential), more preferably ethylene and a C6 to C10
.alpha.-olefin. The C4 to C10 .alpha.-olefin used in
copolymerization with ethylene includes 1-butene, 1-hexene,
4-methyl-1-pentene, 1-octene, 1-decene etc.
The ethylene-based polymer has the following properties [k1] to
[k3].
[k1] The melt flow rate (MFR) is in the range of 1.0 to 50 g/10
minutes, preferably 2.0 to 50 g/10 minutes, more preferably 4.0 to
50 g/10 minutes.
When the melt flow rate (MFR) is not lower than 1.0 g/10 minutes,
the shearing viscosity of the resulting ethylene-based polymer is
not too high and is excellent in moldability. When the melt flow
rate (MFR) is not higher than 50 g/10 minutes, the resulting
ethylene-based polymer is excellent in tensile strength.
The melt flow rate (MFR) depends highly on molecular weight, and as
the melt flow rate (MFR) is decreased, the molecular weight is
increased, while as the melt flow rate (MFR) is increased, the
molecular weight is decreased. It is known that the molecular
weight of the ethylene-based polymer is determined by the
compositional ratio of hydrogen to ethylene (hydrogen/ethylene) in
the polymerization system (for example, Kazuo Soga, KODANSHA
"CATALYTICOLEFINPOLYMERIZATION", p. 376 (1990)). Accordingly,
hydrogen/ethylene is increased or decreased, whereby an
ethylene-based polymer having a melt flow rate (MFR) in the upper
and lower limits in the claims can be produced.
The melt flow rate (MFR) is measured under the conditions of
190.degree. C. and 2.16 kg loading according to ASTM D1238-89.
[k2] LNR is in the range of 0.6 to 1.4, preferably 0.7 to 1.3, more
preferably 0.8 to 1.2.
When LNR is 1.4 or less, the resulting ethylene-based polymer is
excellent in neck-in. As used herein, neck-in refers to a reduction
of the width of a product relative to the width of a dice lip
opening in T-die molding.
LNR depends highly on the ratio of the molecular weight of the
ethylene-based polymer polymerized in <former stage> to the
molecular weight of the ethylene-based polymer polymerized in
<latter stage> (<former stage> molecular
weight/<latter stage> molecular weight) in the production
process shown in Example 1; as (<former stage> molecular
weight/<latter stage> molecular weight) is increased, LNR
tends to be decreased, while as (<former stage> molecular
weight/<latter stage> molecular weight) is decreased, LNR
tends to be increased. It is known that the molecular weight of the
ethylene-based polymer is determined by the compositional ratio of
hydrogen to ethylene (hydrogen/ethylene) in the polymerization
system (for example, Kazuo Soga, KODANSHA "CATALYTIC OLEFIN
POLYMERIZATION", p. 376 (1990)). Accordingly, hydrogen/ethylene is
regulated to increase or decrease (<former stage> molecular
weight/<latter stage> molecular weight), whereby an
ethylene-based polymer having LNR in the upper and lower limits in
the claims can be produced.
LNR is determined by the ratio of neck-in upon molding of a
measurement sample through a small slit dice into a film to neck-in
upon molding of polyethylene (trade name: MIRASON M11, produced by
high-pressure radical polymerization, commercially available from
Mitsui Chemicals, Inc.) into a film in the same manner. LNR is
measured by using an apparatus including (a) a capillary rheometer,
(b) a slit dice, (c) a cooling roll, air nozzle, and (d) a wind-up
roll.
The capillary rheometer (a) plays a role in extruding a molten
resin. As the capillary rheometer, a capillary rheometer
(Capillograph 1B (barrel diameter 10 mm.phi.)) manufactured by Toyo
Seiki Seisaku-sho, Ltd. was used under the conditions of a barrel
temperature of 200.degree. C. and a piston speed of 50 mm/min. 20 g
measurement sample was used in each measurement, and the melting
time was 6 minutes.
A top view of the slit dice (b) is shown in FIG. 1, a side view
thereof is shown in FIG. 2, and an A B sectional view is shown in
FIG. 3. The slit dice, which is butted with fixing bolt (2), was
fixed below a barrel of the capillary rheometer via an inserted
nozzle and an adaptor connected to a joint (1), and heated by a
plate heater to 200.degree. C. ((3) in FIG. 2 is a part where a
thermocouple is inserted).
A front view of the cooling roll, air nozzle (c) is shown in FIG. 4
and a side view thereof is shown in FIG. 5. The cooling roll (4)
and air nozzle (5) are arranged below the slit dice and fixed such
that the distance between the lower end of the slit dice and the
upper end of the cooling roll (4) is 10 mm. The air nozzle is 26 cm
in length, and is provided with air-blowing openings of 1 mm in
diameter at 5.5 mm intervals. The flow rate of cooling air was
under the conditions of 50 L/min.
The measurement sample was molded into a film by the above
apparatus, and 1.75 m to 1.95 mm film was sampled from the terminal
of the film. The neck-in (C) of the measurement sample is
determined from a value obtained by subtracting the width of the
sampled film from the width (40 mm) of the slit dice. The width of
the film was measured at 3 arbitrary points, and the average width
was used. The neck-in (d) of polyethylene (trade name: MIRASON M11)
produced by high-pressure radical polymerization, commercially
available from Mitsui Chemicals, Inc. is also determined in the
same manner as above. LNR is determined by the following equation
(Eq-3): LNR=C/D (Eq-3)
[k3] Take-up speed at break [DS (m/min)] at 160.degree. C. and melt
flow rate (MFR) satisfy the following relationship (Eq-1):
12.times.MFR.sup.0.577.ltoreq.DS.ltoreq.165.times.MFR.sup.0.577
(Eq-1)
Preferably, the following relationship (Eq-4) is satisfied:
17.times.MFR.sup.0.577.ltoreq.DS.ltoreq.53.times.MFR.sup.0.577
(Eq-4)
More preferably, the following relationship (Eq-5) is satisfied:
17.times.MFR.sup.0.577.ltoreq.DS.ltoreq.40.times.MFR.sup.0.577
(Eq-5)
When the take-up speed at break (DS) is 17.times.MFR.sup.0.577 or
more, the resulting ethylene-based polymer is excellent in
high-speed film processability.
The take-up speed at break (DS) depends on the amount of the
components in the ethylene-based polymer polymerized in <former
stage> and the amount of the components in the ethylene-based
polymer polymerized in <latter stage> (<former stage>
component amount/(<latter stage> component amount), in the
production process shown in Example 1; as (<former stage>
component amount/(<latter stage> component amount) is
increased, the take-up speed at break (DS) in the same melt flow
rate (MFR) is decreased, while as (<former stage> component
amount/(<latter stage> component amount) is decreased, the
take-up speed at break (DS) in the same melt flow rate (MFR) is
increased. Accordingly, the polymerization time in <former
stage> and the polymerization time in <latter stage> in
the production process shown in Example 1 are regulated to increase
or decrease (<former stage> component amount/(<latter
stage> component amount), whereby an ethylene-based polymer
satisfying the relationship between take-up speed at break (DS) and
melt flow rate (MFR) in the claims can be produced.
The take-up speed at break (DS) is determined by the take-up speed
upon breakage of the ethylene-based polymer stretched by taking up
the melted ethylene-based polymer at a varying take-up speed. In
this measurement, a capillary rheometer (Capillograph 1B (barrel
diameter, 10 mm.phi.) manufactured by Toyo Seiki Seisaku-sho, Ltd.)
was used. The measurement was conducted under conditions where the
resin temperature was 160.degree. C., the melting time was 6
minutes, the barrel diameter was 10 mm.phi., the extrusion speed
was 15 mm/min., the capillary diameter was 2.00 mm.phi., the
capillary length was 10 mm, the take-up speed was 15 to 400 m/min.
, and the take-up acceleration was 100 m/min.sup.2. When bubbles
etc. are present in the ethylene-based polymer, the take-up speed
at break (DS) may be significantly reduced. Accordingly, the
measurement was conducted 7 times, and the average of higher 3
take-up speeds among the measurements was indicated as the take-up
speed at break (DS).
The ethylene-based polymer according to the present invention
preferably satisfies the following requirements [m1] to [m3] in
addition to the requirements described above.
[m1] Density (d) is in the range of 890 to 950 kg/m.sup.3,
preferably 900 to 940 kg/m.sup.3, more preferably 905 to 935
kg/m.sup.3.
When the density (d) is not lower than 890 kg/m.sup.3, the
resulting ethylene-based polymer is excellent in heat resistance,
while when the density (d) is not higher than 950 g/m.sup.3, the
resulting ethylene-based polymer is excellent in low-temperature
sealing properties.
The density depends on the content of .alpha.-olefin in the
ethylene-based polymer, and as the content of .alpha.-olefin is
decreased, the density is increased, while the content of
.alpha.-olefin is increased, the density is decreased. It is known
that the content of .alpha.-olefin in the ethylene-based polymer is
determined by the compositional ratio of .alpha.-olefin to ethylene
(.alpha.-olefin/ethylene) in the polymerization system (for
example, Walter Kaminsky, Makromol. Chem., 193, p. 606 (1992)).
Accordingly, .alpha.-olefin/ethylene is increased or decreased,
whereby an ethylene-based polymer having density in the upper and
lower limits in the claims can be produced.
The density (d) was measured by thermally treating a measurement
sample at 120.degree. C. for 1 hour, then gradually cooling it
linearly to room temperature over 1 hour and measuring its density
in a density gradient tube.
[m2] Ratio [MT/.eta.* (g/Poise) of melt tension [MT (g)] to
shearing viscosity [.eta.* (Poise)] at 200.degree. C. at an angular
rate of 1.0 rad/sec. is in the range of 2.00.times.10.sup.-4 to
9.00.times.10.sup.-4, preferably 2.30.times.10.sup.-4 to
9.00.times.10.sup.-4, more preferably 3.00.times.10.sup.-4 to
9.00.times.10.sup.-4.
When MT/.eta.* is not lower than 2.00.times.10.sup.-4, the
resulting ethylene-based polymer is excellent in neck-in.
MT/.eta.* depends highly on the ratio of the molecular weight of
the ethylene-based polymer polymerized in <former stage> to
the molecular weight of the ethylene-based polymer polymerized in
<latter stage> (<former stage> molecular
weight/<latter stage> molecular weight), in the production
process shown in Example 1; as (<former stage> molecular
weight/<latter stage> molecular weight) is increased,
MT/.eta.* is increased, while as (<former stage> molecular
weight/<latter stage> molecular weight) is decreased,
MT/.eta.* is decreased. It is known that the molecular weight of
the ethylene-based polymer is determined by the compositional ratio
of hydrogen to ethylene (hydrogen/ethylene) in the polymerization
system (for example, Kazuo Soga, KODANSHA "CATALYTIC OLEFIN
POLYMERIZATION", p. 376 (1990)). Accordingly, hydrogen/ethylene is
regulated to increase or decrease (<former stage> molecular
weight/<latter stage> molecular weight), whereby an
ethylene-based polymer having MT/.eta.* in the upper and lower
limits in the claims can be produced.
The melt tension (MT) is determined by measuring the stress upon
stretching a molten polymer at a constant speed. In this
measurement, a MT measuring machine manufactured by Toyo Seiki
Seisaku-sho, Ltd. was used. The measurement was conducted under
conditions where the resin temperature was 190.degree. C., the
melting time was 6 minutes, the barrel diameter was 9.55 mm.phi.,
the extrusion speed was 15 mm/min., the take-up speed was 10 to 20
m/min., the nozzle diameter was 2.095 mm.phi., and the nozzle
length was 8 mm.
The shearing viscosity (*.eta.) at 200.degree. C. at an angular
velocity of 1.0 rad/sec. is determined by measuring the angular
velocity [.omega. (rad/sec)] dispersion of shearing viscosity
(*.eta.) at a measurement temperature of 200.degree. C. in the
range of 0.02512.ltoreq..omega..ltoreq.400. In this measurement,
Rheometer RDS-II manufactured by Rheometrix was used. In a sample
holder, 25 mm.phi. parallel plate was used, and the sample
thickness was about 1.8 mm. 5 points were measured per digit of
.omega.. Distortion was selected suitably in the range of 10 to 30%
so as not to be over torque so that torque could be detected in the
measurement range. The sample used in measurement of shearing
viscosity was prepared by press-molding the measurement sample to a
thickness of 2 mm under the conditions of a preheating temperature
of 190.degree. C., a preheating time of 5 minutes, a heating
temperature of 190.degree. C., a heating time of 2 minutes, a
heating pressure of 100 kg/cm.sup.2, a cooling temperature of
20.degree. C., a cooling time of 5 minutes and a cooling pressure
of 100 kg/cm.sup.2 with a press molding machine manufactured by
Shinto Metal Industries, Ltd.
[m3] The sum [(A+B) (/1000C)] of the number of methyl branches [A
(/1000C)] and the number of ethyl branches [B (1000C)] measured by
.sup.13C-NMR is 1.4 or less, preferably 1.0 or less, more
preferably 0.6 or less. The number of methyl branches and the
number of ethyl branches defined in the present invention is
defined in terms of number per 1000 carbons as defined later.
It is known that when short branches such as methyl branches, ethyl
branches etc. occur in the ethylene-based polymer, the short
branches are incorporated into crystals to broaden the spacing of
the crystals, thus lowering the mechanical strength of the resin
(for example, Zenjiro Ohsawa, et al: Kobunshi No Jyumyoyosoku To
Chojyumyoka Gijyutsu (Estimation of Longevity of Polymer and
Techniques of Pronging Longevity), p. 481, N.T.S (2002)).
Accordingly, when the sum (A+B) of the number of methyl branches
and the number of ethyl branches is 1.4 or less, the resulting
ethylene-based polymer is excellent in mechanical strength.
The number of methyl branches and the number of ethyl branches
depend highly on the method of polymerizing the ethylene-based
polymer, and the ethylene-based polymer obtained by high-pressure
radical polymerization has more methyl and ethyl branches than
those in an ethylene-based polymer obtained by coordination
polymerization using a Ziegler catalyst system. In the coordination
polymerization, the number of methyl branches and the number of
ethyl branches in the ethylene-based polymer, depend highly on the
compositional ratio among propylene, 1-butene, and ethylene
(propylene/ethylene, 1-butene/ethylene) in the polymerization
system. Accordingly, 1-butene/ethylene can be regulated to produce
an ethylene-based polymer having the sum (A+B) of the number of
methyl branches and the number of ethyl branches in the claims.
The number of methyl branches and the number of ethyl branches
measured by .sup.13C-NMR are determined as follows. Measurement was
conducted with an integration frequency of 10,000 to 30,000 by
using ECP500 nuclear magnetic resonance apparatus (1H: 500 MHz)
manufactured by JEOL. As a chemical shift standard, a peak (29.97
ppm) of main-chain methylene was used. 250 to 400 mg PE sample and
3 ml mixture consisting of o-dichlorobenzene (special grade,
manufactured by Wako Pure Chemical Industries, Ltd.) and benzene-d6
(manufactured by ISOTEC) in the 5/1 ratio (ratio by volume) were
introduced into a commercial quartz glass tube of 10 mm in diameter
for NMR measurement, then heated at 120.degree. C. and dispersed
uniformly. Assignment of each absorption in an NMR spectrum was
conducted according to Kagaku no Ryoiki (Chemical Field), extra
volume 141, NMR--General Remarks and Experimental Guide [I], pages
132 to 133. The number of methyl branches per 1,000 carbons was
calculated from the integrated intensity ratio of the absorption
(19.9 ppm) of methyl groups derived from methyl branches to the
total integration of absorption appearing in the range of 5 to 45
ppm. The number of ethyl branches was calculated from the
integrated intensity ratio of the absorption (10.8 ppm) of ethyl
groups derived from ethyl branches to the total integration of
absorption appearing in the range of 5 to 45 ppm.
The ethylene-based polymer according to the present invention
preferably satisfies at least one of the following [n1] to [n3] in
addition to the requirements described above.
[n1] The ratio (Mz/Mw) of Z-average molecular weight (Mz) to
weight-average molecular weight (Mw), both of which were measured
by GPC, is preferably 10 or more, preferably 20 or more, still more
preferably 30 or more. When Mz/Mw is 10 or more, the resulting
ethylene-based polymer has high melt tension and is excellent in
moldability.
Mz/Mw is increased with an increase in the difference between the
molecular weight of the ethylene-based polymer polymerized in
<former stage> and the molecular weight of the ethylene-based
polymer polymerized in <latter stage>, in the production
process shown in Example 1, while Mz/Mw is decreased with a
decrease in the difference therebetween. It is known that the
molecular weight of the ethylene-based polymer is determined by the
compositional ratio of hydrogen to ethylene (hydrogen/ethylene) in
the polymerization system (for example, Kazuo Soga, KODANSHA
"CATALYTIC OLEFIN POLYMERIZATION", p. 376 (1990)). Accordingly,
hydrogen/ethylene is regulated to increase or decrease the ratio of
the molecular weight of the ethylene-based polymer polymerized in
<former stage> to the molecular weight of the ethylene-based
polymer polymerized in <latter stage>, whereby an
ethylene-based polymer having Mz/Mw in the upper and lower limits
in the claims can be produced.
The Z-average molecular weight (Mz) and average-molecular weight
(Mw) were measured in the following manner by using GPC-150C
manufactured by Waters. As columns for separation, TSK gel GMH6-HT
and TSK gel GMH6-HTL were used, and their column sizes were 7.5 mm
in inner diameter and 600 mm in length respectively, and the column
temperature was 140.degree. C., and o-dichlorobenzene (Wako Pure
Chemical Industries, Ltd.) was used as the mobile phase and
transferred at 1.0 ml/min. with 0.025 wt % BHT (Takeda Chemical
Industries, Ltd.) as an antioxidant. The concentration of a sample
was 0.1 wt %, and the volume of the sample injected was 500 .mu.L,
and a differential refractometer was used as the detector. Standard
polystyrene having a molecular weight of Mw.ltoreq.1000 and
Mw.gtoreq.4.times.10.sup.6 was a product of Tosoh Corporation, and
standard polystyrene having a molecular weight of
1000.ltoreq.Mw.ltoreq.4.times.10.sup.6 was a product of Pressure
Chemical. The molecular weight is a value determined using
universal calibration with PE as the standard.
[n2] The number of terminal vinyl groups (V) per molecular chain
calculated from the number of terminal vinyl groups [v (/1000C)]
per 1000 carbon atoms measured by IR and number-average molecular
weight (Mn) measured by GPC is not higher than 0.47/molecular
chain, preferably not higher than 0.30/molecular chain, still more
preferably not higher than 0.16/molecular chain. When the number of
terminal vinyl groups (V) per molecular chain is not higher than
0.47/molecular chain, the resulting ethylene-based polymer is
excellent in thermal stability at the time of molding
processing.
The number of terminal vinyl groups (V) per molecular chain depends
highly on the compositional ratio of hydrogen to ethylene
(hydrogen/ethylene) in the polymerization system, and as
hydrogen/ethylene is increased, the number of terminal vinyl groups
(V) per molecular chain is decreased, while as hydrogen/ethylene is
decreased, the number of terminal vinyl groups (V) per molecular
chain is increased. Accordingly, hydrogen/ethylene in <former
stage> in the production process shown in Example 1 is increased
or decreased, whereby an ethylene-based polymer having the number
of terminal vinyl groups (V) per molecular chain in the claims can
be produced.
Using the number-average molecular weight (Mn) measured by GPC and
the number of terminal vinyl groups (v) per 1000 carbon atoms
measured by IR, the number of terminal vinyl groups (V) per
molecular chain is determined by the following equation (Eq-6):
V=Mn.times.v/14,000 (Eq-6)
The number-average molecular weight (Mn) was measured in the same
manner as described above by usingGPC-15oC manufactured by
Waters.
The number (v) of terminal vinyl groups per 1000 carbon atoms was
measured in the following manner by using an infrared
spectrophotometer FT-IR 410 manufactured by Nippon Bunko Co., Ltd.
About 0.3 g ethylene-based polymer was sandwiched with a Teflon
sheet (0.1 mm in thickness), an aluminum plate (0.1 mm in
thickness) and an iron plate (2 to 3 mm in thickness) in this order
and pressed at a molding pressure of 50 to 100 kg/cm.sup.2 at a
heating temperature of 180.degree. C. for a heating time of 3
minutes in a hydraulic molding machine and then cooled at room
temperature for 1 minute at a pressure of 0 to 50 kg/cm.sup.2 to
prepare a measurement sample. Measurement was carried out in the
measurement range of 5000 cm.sup.-1 to 400 cm.sup.-1 with a
resolution of 2 cm.sup.-1 and the integration frequency of 4 by a
transmission method. From a calibration curve prepared using
unsaturated bond-free polyethylene and polyethylene having all
vinyl group at one end, the number of terminal vinyl groups per
1000 carbon atoms [v (/1000C)] was quantified using, as a key band,
an absorption derived from terminal vinyl group detected at 910
cm.sup.-1.
[n3] Melting-point maximum peak [Tm (.degree. C.)] in DSC and
density (d) satisfy the following relationship (Eq-2):
(0.315.times.d)-200.ltoreq.Tm.ltoreq.(0.315.times.d)-170 (Eq-2)
More preferably, the following relationship (Eq-7) is satisfied:
(0.315.times.d)-200.ltoreq.Tm.ltoreq.(0.315.times.d)-173 (Eq-7)
When the melting-point maximum peak (Tm) is lower than
(0.315.times.d)-170, the resulting ethylene-based polymer is
excellent in low-temperature sealing properties.
The melting-point maximum peak (Tm) depends not only density (d)
but also on the distribution of .alpha.-olefins (compositional
distribution) among molecular chains of the resulting
ethylene-based polymer. When the density is the same, a broader
compositional distribution gives rise to thicker crystals with
molecular chains with less .alpha.-olefin, thus increasing the
melting-point maximum peak (Tm), while with a narrower
compositional distribution given, molecular chains with uniform
.alpha.-olefin occur and thick crystals are not formed, and thus
the melting-point maximum peak (Tm) is lowered. In the case of the
Ziegler catalyst, the active site is heterogeneous, and thus the
compositional distribution of the resulting ethylene-based polymer
is known to be broad (for example, Kazuo Matsuura et al.:
Polyethylene Gijutsu Dokuhon (Technical Book of Polyethylene), p.
20, (2001), Kogyo Chosakai Publishing Co., Ltd.). Accordingly, when
the density of the ethylene-based polymer is the same, the
melting-point maximum peak (Tm) is increased. In the case of the
metallocene catalyst, the active site is homogeneous so that the
compositional distribution of the resulting ethylene-based polymer
is narrowed, and as a result, when the density is the same, the
melting-point maximum peak (Tm) is decreased. The melting-point
maximum peak (Tm) at the same density can also be changed by
polymerization temperature. When the polymerization temperature is
increased, the polymerization system tends to become uniform to
narrow the compositional distribution. As a result, the
melting-point maximum peak (Tm) at the same density is decreased.
When the polymerization temperature is decreased, the
polymerization systemtends to become heterogeneous to broaden the
compositional distribution. As a result, the melting-point maximum
peak (Tm) at the same density is increased. Accordingly, the
polymerization temperature in <latter stage> in the
production process shown in Example 1 is increased or decreased,
whereby an ethylene-based polymer satisfying the relationship
between the melting-point maximum peak (Tm) and the density (d) in
the claims can be produced.
Using Pyris 1 manufactured by PERKIN ELMER, the melting-point
maximum peak (Tm) was measured in the following manner. The sample
used in measurement was prepared by press-molding a measurement
sample to a thickness of 2 mm under the conditions of a preheating
temperature of 190.degree. C., a preheating time of 5 minutes, a
heating temperature of 190.degree. C., a heating time of 2 minutes,
a heating pressure of 100 kg/cm.sup.2, a cooling temperature of
20.degree. C., a cooling time of 5 minutes and a cooling pressure
of 100 kg/cm.sup.2 with a press molding machine manufactured by
Shinto Metal Industries, Ltd. The measurement sample, about 5 mg,
was placed in an aluminum pan and measured in a nitrogen atmosphere
(nitrogen: 20 ml/min) by the following temperature profiles [1] to
[3]: [1] The temperature was increased from30.degree. C. at
10.degree. C./min. to 200.degree. C., [2] The temperature was kept
at 200.degree. C. for 5 minutes and then decreased at 20.degree.
C./min. to 30.degree. C., and [3] The temperature was increased
from 30.degree. C. at 10.degree. C./min. to 200.degree. C.
The temperature of the maximum peak in an endothermic curve
obtained in [3] was indicated as the melting-point maximum peak (Tm
(.degree. C.)).
(2) Polymerization Catalyst for Producing the Ethylene-based
Polymer
The ethylene-based polymer of the present invention can be produced
in a single-stage polymerization system or in a multi-stage (two or
more stage) polymerization system. As described above, usually a
multi-stage (preferably two- or three-stage) polymerization
reaction system is used in the multi-stage polymerization system.
The multi-stage polymerization in the present invention is composed
of a former-stage polymerization (also referred to hereinafter as
"pre-polymerization" or "preliminary polymerization") as the first
polymerization step and a latter-stage polymerization including
second and subsequent stages (also referred to hereinafter as
"polymerization"). An ethylene-based polymer obtained by
(co)polymerizing ethylene, or ethylene and a C4 to C10
.alpha.-olefin, by using a prepolymer obtained under specific
conditions (also referred to hereinafter as "preliminary polymer")
as the polymerization catalyst also constitutes one aspect of the
present invention. That is, the ethylene-based polymer of the
present invention can be produced by (co)polymerizing ethylene, or
ethylene and a C4 to C10 .alpha.-olefin, in the presence of any one
of the following four polymerization catalysts (C-1) to (C-4),
among which the third olefin polymerization catalyst (C-3) and the
fourth olefin polymerization catalyst (C-4) are preferable, and
particularly the fourth olefin polymerization catalyst (C-4) is a
preferable catalyst.
The first olefin polymerization catalyst (C-1) according to the
present invention comprises:
a solid carrier,
(A) a solid transition metal catalyst component obtained by
contacting (a) a compound of a transition metal of the group 4 in
the periodic table, containing at least one ligand having a
cyclopentadienyl skeleton, (b) an organoaluminum oxy compound, and
(c) a multifunctional organic halide component represented by the
following general formula (I): (Q.sup.1).sub.o--R--(Q.sup.2).sub.p
(I) wherein R is a (o+p)-valent group containing at least one
halogen atom, o and p each represent a positive integer satisfying
the relationship (o+p).gtoreq.2, Q.sup.1 and Q.sup.2 each represent
--OH, --NH.sub.2 or --NLH whereupon L is an arbitrary group
selected from a C1 to C20 hydrocarbon group, a C1 to C20
halogen-containing hydrocarbon group, a silicon-containing group,
an oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group and a phosphorus-containing group, and L
and R, N and R, or N and N may be bound to each other to form a
ring, and if necessary
(B) An Organoaluminum Compound.
The second olefin polymerization catalyst (C-2) according to the
present invention comprises a solid carrier, (A) a solid catalyst
component obtained by contacting (a) a compound of a transition
metal of the group 4 in the periodic table, containing at least one
ligand having a cyclopentadienyl skeleton, (b) an organoaluminum
oxy compound, (c) a multifunctional organic halide component
represented by the general formula (I), and (d) an organoaluminum
compound, and if necessary (B) an organoaluminum compound.
The third olefin polymerization catalyst (C-3) according to the
present invention comprises a prepolymer obtained by
pre-polymerizing the solid transition metal catalyst component
constituting the olefin polymerization catalyst (C-1), with
ethylene, or ethylene/.alpha.-olefin, wherein 0.01 to 1000 g
prepolymer having a z-average molecular weight of 6,000,000 or more
by GPC and having a die-swell ratio of 1.4 or more, is contained
per g of the solid transition metal catalyst component, and if
necessary (B) an organoaluminum compound.
The fourth olefin polymerization catalyst (C-4) according to the
present invention comprises a prepolymer obtained by
pre-polymerizing the solid transition metal catalyst component
constituting the olefin polymerization catalyst (C-2), with
ethylene, orethylene/.alpha.-olefin, wherein 0.01 to 1000 g
prepolymer having a z-average molecular weight of 6,000,000 or more
by GPC and having a die-swell ratio of 1.4 or more, is contained
per g of the solid transition metal catalyst component, and if
necessary (B) an organoaluminum compound.
Hereinafter, the olefin polymerization catalyst according to the
present invention and a process for producing an olefin by using
the olefin polymerization catalyst are specifically described. In
the present invention, the term "polymerization" maybe used to mean
not only homopolymerization but also copolymerization, and the term
"polymer" may be used to mean not only homopolymer but also
copolymer.
First, the respective components used in the olefin polymerization
catalyst of the present invention are described. In the present
invention, (a) a compound of a transition metal of the group 4 in
the periodic table, containing at least one ligand having a
cyclopentadienyl skeleton, (also referred to hereinafter as
component (a)) is a transition metal compound represented by the
following general formula (V): MG.sup.1.sub.x (V) wherein M is a
transition metal atom selected from the group 4 in the periodic
table, G represents a ligand coordinated with a transition metal
atom, and at least one G.sup.1 is a ligand having a
cyclopentadienyl skeleton, G.sup.1 other than the ligand having a
cyclopentadienyl skeleton is a hydrocarbon group, an alkoxy group,
an aryloxy group, a trialkylsilyl group, an SO.sub.3J group (J is a
C1 to C8 hydrocarbon group which may have a substituent group such
as halogen), a halogen atom or a hydrogen atom, and x represents
the valance of a transition metal. In the general formula (V), M is
a transition metal atom selected from the group 4 in the periodic
table, and is specifically a zirconium atom, titanium atom or
hafnium atom, preferably a zirconium atom.
The ligand having a cyclopentadienyl skeleton can be exemplified
by, for example, an alkyl-substituted cyclopentadienyl group such
as cyclopentadienyl group, methyl cyclopentadienyl group, dimethyl
cyclopentadienyl group, trimethyl cyclopentadienyl group,
tetramethyl cyclopentadienyl group, pentamethyl cyclopentadienyl
group, ethyl cyclopentadienyl group, methylethyl cyclopentadienyl
group, propyl cyclopentadienyl group, methylpropyl cyclopentadienyl
group, butyl cyclopentadienyl group, methylbutyl cyclopentadienyl
group, hexyl cyclopentadienyl group etc.; or an indenyl group,
2-methyl indenyl, 2-ethyl indenyl group, 2-n-propyl indenyl group,
2-phenyl indenyl group, 4-phenyl indenyl group, 2-methyl-4-phenyl
indenyl group, 2-methyl-4,6-di-i-propyl indenyl group,
2-methyl-4,5-benzoindenyl group, 4,5,6,7-tetrahydroindenyl group,
fluorenyl group, 9-methyl fluorenyl group, 2, 7-dimethyl fluorenyl
group, 2,7-di-t-butyl fluorenyl group etc. These groups may be
substituted with a halogen atom, a trialkylsilyl group etc.
When the compound represented by the general formula (V) contains
two or more ligands each having a cyclopentadienyl skeleton, two of
the ligands each having a cyclopentadienyl skeleton may be bound to
each other via methylene, diisopropyl methylene, methyl-t-butyl
methylene, dicyclohexyl methylene, methylcyclohexyl methylene,
methyl phenyl methylene, diphenyl methylene, methyl naphthyl
methylene, dinaphthyl methylene, ethylene, propylene,
isopropylidene, cyclopropylidene, cyclobutylidene,
cyclopentylidene, cyclohexylidene, cycloheptylidene, bicycle[3.3.1]
nonylidene, norbornylidene, adamantylidene,
tetrahydronaphthylidene, dihydroindanylidene, chloroethylene group,
chloromethylene group, silylene, methyl silylene, dimethyl
silylene, diisopropyl silylene, methyl-t-butyl silylene,
dicyclohexyl silylene, methyl cyclohexyl silylene, methyl phenyl
silylene, diphenyl silylene, methyl naphthyl silylene, dinaphthyl
silylene, cyclodimethylene silylene, cyclotrimethylene silylene,
cyclotetramethylene silylene, cyclopentamethylene silylene,
cycloxamethylene silylene, cycloheptamethylene silylene, or a
germanium-containing group or a tin-containing group wherein in the
above silicon-containing group, silicon was converted into
germanium or tin.
The ligand G.sup.1 other than the ligand having a cyclopentadienyl
skeleton is specifically as follows. The hydrocarbon group
represented by the ligand G.sup.1 includes an alkyl group,
cycloalkyl group, aryl group and aralkyl group, and specifically
the alkyl group is exemplified by a methyl group, ethyl group,
propyl group, isopropyl group, butyl group etc., the cycloalkyl
group is exemplified by a cyclopentyl group, cyclohexyl group etc.,
the aryl group is exemplified by a phenyl group, tolyl group etc.,
and the aralkyl group is exemplified by a benzyl group, neophyl
group etc. The alkoxy group is exemplified by a methoxy group,
ethoxy group, butoxy group etc., the aryloxy group is exemplified
by a phenoxy group etc., and the halogen is exemplified by
fluorine, chlorine, bromine, iodine etc.
The ligand represented by SO.sub.3J includes, for example, a
p-toluenesulfonato group, methanesulfonato group,
trifluoromethanesulfonato group etc. The compound of a transition
metal containing the ligand having a cyclopentadienyl skeleton, for
example where the valance of the transition metal is 4, is
represented more specifically by the following general formula
(Va): G.sup.2.sub.kG.sup.3.sub.lG.sup.4.sub.mG.sup.5.sub.nM (Va)
wherein M represents a transition metal atom selected from the
group 4 in the periodic table, G.sup.2 represents a group (ligand)
having a cyclopentadienyl skeleton, G.sup.3, G.sup.4 and G.sup.5
each represent a group (ligand) having a cyclopentadienyl skeleton
or an alkyl group, a cycloalkyl group, an aryl group, an aralkyl
group, an alkoxy group, an aryloxy group, a trialkylsilyl group, an
SO.sub.3J group, a halogen atom or a hydrogen atom, k is an integer
of 1 or more, and k+l+m+n=4.
In the present invention, the transition metal compound represented
by the general formula (Va) above includes the compounds wherein at
least one of G.sup.3, G.sup.4and G.sup.5 is a group (ligand) having
a cyclopentadienyl skeleton, for example the compounds wherein each
of G.sup.2 and G.sup.3 is a group (ligand) having a
cyclopentadienyl skeleton. In such compounds, two of the groups
(ligands) each having a cyclopentadienyl skeleton may be bound to
each other via an alkylene group such as methylene, ethylene,
propylene or the like, a substituted alkylene group such as
diisopropyl methylene, methyl-t-butyl methylene, dicyclohexyl
methylene, methylcyclohexyl methylene, methyl phenyl methylene,
diphenyl methylene, methyl naphthyl methylene, dinaphthyl
methylene, isopropylidene or the like, a cycloalkylene group such
as cyclopropylidene, cyclobutylidene, cyclopentylidene,
cyclohexylidene, cycloheptylidene, bicycle [3.3.1] nonylidene,
norbornylidene, adamantylidene, tetrahydronaphthylidene,
dihydroindanylidene or the like, a halogen-containing alkylene
group such as chloroethylene, chloromethylene or the like, a
(substituted) silylene group such as silylene, methyl silylene,
dimethyl silylene, diisopropyl silylene, methyl-t-butyl silylene,
dicyclohexyl silylene, methyl cyclohexyl silylene, methyl phenyl
silylene, diphenyl silylene, methyl naphthyl silylene, dinaphthyl
silylene, cyclodimethylene silylene, cyclotrimethylene silylene,
cyclotetramethylene silylene, cyclopentamethylene silylene,
cycloxamethylene silylene, cycloheptamethylene silylene or the
like, or a germanium-containing group or a tin-containing group
wherein in the above silicon-containing group, silicon was
converted into germanium or tin. When each of G.sup.2and G.sup.3 is
a group (ligand) having a cyclopentadienyl skeleton, each of
G.sup.4and G.sup.5is a group having a cyclopentadienyl skeleton or
an alkyl group, a cycloalkyl group, an aryl group, an aralkyl
group, an alkoxy group, an aryloxy group, a trialkylsilyl group, an
SO.sub.3J group, a halogen atom or a hydrogen atom.
Among the transition metal compounds containing two or more groups
(ligands) having a cyclopentadienyl skeleton, at least one
component selected from the following components (a-1), (a-2) and
(a-3) is preferably used.
The components (a-1) and (a-2) are transition metal compounds
represented by the general formulae (II) and (III)
respectively:
##STR00003## wherein R.sup.1 to R.sup.6 are independently selected
from a hydrogen atom, a halogen atom, a C1 to C20 alkyl group, a C3
to C20 cycloalkyl group, a C2 to C20 alkenyl group, a C6 to C20
aryl group, and a C7 to C20 arylalkyl group, respectively, and can
contain a silicon, halogen or germanium atom, and at least one pair
of R.sup.3 and R.sup.4, R.sup.4 and R.sup.5, and R.sup.5 and
R.sup.6 may be bound to each other to form a ring, R.sup.7 is a
divalent group bounding two ligands, and is a C1 to C20 hydrocarbon
group, a C1 to C20 halogen-containing hydrocarbon group, a
silicon-containing group or a germanium- or tin-containing group,
and two substituent groups on the same carbon, silicon, germanium
or tin atom may be bound to each other to form a ring, t.sup.1 and
t.sup.2independently represent a group selected from a hydrogen
atom, a halogen atom, a C1 to C20 hydrocarbon group, a C1 to C20
halogen-containing hydrocarbon group, a silicon-containing group,
an oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group and a phosphorus-containing group,
respectively, and M is a transition metal selected from titanium,
zirconium and hafnium.
Among the groups represented by R.sup.1 to R.sup.6 in the general
formulae (II) and (III), the halogen atom includes chlorine,
bromine, fluorine and iodine atoms; the C1 to C20 alkyl group
includes, for example, a methyl group, ethyl group, n-propyl group,
isopropyl group, n-butyl group, isobutyl group, s-butyl group,
t-butyl group, n-pentyl group, neopentyl group, n-hexyl group,
octyl group, nonyl group, dodecyl group, eicosyl group, norbornyl
group, adamantyl group etc.; the C3 to C20 cycloalkyl group
includes a cyclopropyl group, cyclobutyl group, cyclopentyl group,
cyclohexyl group etc.; the C2 to C20 alkenyl group includes a vinyl
group, propenyl group, cyclohexenyl group etc.; the C7 to C20
arylalkyl group includes benzyl, phenylethyl, phenylpropyl etc.;
and the C6 to C20 aryl group includes phenyl, tolyl,
dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl,
biphenyl, .alpha.- or .beta.-naphthyl, methylnaphthyl, anthracenyl,
phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenarenyl,
aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl etc.
The halogen-containing group represented by R.sup.1 to R.sup.6
includes groups wherein in the above-mentioned alkyl group,
cycloalkyl group, alkenyl group, arylalkyl group and aryl group,
one or more hydrogen atoms were replaced by suitable halogen
atoms.
The silicon- or germanium-containing group includes groups wherein
in the above-mentioned alkyl group, cycloalkyl group, alkenyl
group, arylalkyl group and aryl group, one or more carbon atoms
were replaced by silicon or germanium atoms.
R.sup.1 to R.sup.6 may be the same or different from one another,
and at least one pair of adjacent groups, that is, at least one
pair of R.sup.3 and R.sup.4, R.sup.4 and R.sup.5, and R.sup.5 and
R.sup.6 may be bound to each other to form a ring. The indenyl
group having formed such a ring includes, for example,
4,5-benzoindenyl group, 5,6-benzoindenyl group, 6,7-benzoindenyl
group, .alpha.-acenaphthoindenyl group, and C1 to C10
alkyl-substituted derivatives thereof.
R.sup.7 is a divalent group having two ligands, and the C1 to C20
hydrocarbon group represented by R.sup.7 includes an alkylene group
such as methylene, ethylene, propylene etc., a substituted alkylene
group such as diisopropyl methylene, methyl-t-butyl methylene,
dicyclohexylmethylene, methylcyclohexylmethylene, methyl phenyl
methylene, diphenyl methylene, methyl naphthyl methylene,
dinaphthyl methylene, isopropylidene etc., and a cycloalkylene
group such as cyclopropylidene, cyclobutylidene, cyclopentylidene,
cyclohexylidene, cycloheptylidene, bicycle[3.3.1] nonylidene,
norbornylidene, adamantylidene, tetrahydronaphthylidene,
dihydroindanylidene etc., and the C1 to C20 halogen-containing
hydrocarbon group includes groups wherein in the above hydrocarbon
group, one or more hydrogen atoms were replaced by suitable halogen
atoms.
The C1 to C20 silicon-containing group includes (substituted)
silylene groups such as silylene, methyl silylene, dimethyl
silylene, diisopropyl silylene, methyl-t-butyl silylene,
dicyclohexyl silylene, methylcyclohexyl silylene, methylphenyl
silylene, diphenyl silylene, methyl naphthyl silylene, dinaphthyl
silylene, cyclodimethylene silylene, cyclotrimethylene silylene,
cyclotetramethylene silylene, cyclopentamethylene silylene,
cyclohexamethylene silylene, cycloheptamethylene silylene etc., and
the germanium- or tin-containing group includes groups wherein in
the above silicone-containing group, silicone was replaced by
germanium or tin.
t.sup.1 and t.sup.2 independently represent a group selected from a
hydrogen atom, a halogen atom, a C1 to C20 hydrocarbon group, a C1
to C20 halogen-containing hydrocarbon group, a silicon-containing
group, an oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group and a phosphorus-containing group,
respectively. The halogen atom includes chlorine, bromine, fluorine
and iodine atoms, and the C1 to C20 hydrocarbon group includes, for
example, an alkyl group such as a methyl group, ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group,
t-butyl group, n-hexyl group, n-decyl group etc., an aryl group
such as a phenyl group, 1-naphthyl group, 2-naphthyl group etc.,
and an aralkyl group such as a benzyl group, and the C1 to C20
halogen-containing hydrocarbon group includes groups wherein in the
above hydrocarbon group, one or more hydrogen atoms were replaced
by suitable halogen atoms, for example a trifluoromethy group. The
silicon-containing group includes a trimethyl silyl group, dimethyl
(t-butyl) silyl group etc., the oxygen-containing group includes a
methoxy group, ethoxy group etc., the sulfur-containing group
includes a thiol group, sulfonic acid group etc., the
nitrogen-containing group includes a dimethyl amino group etc., and
the phosphorus-containing group includes a phenyl phosphine group
etc. t.sup.1 and t.sup.2maybe the same or different from each
other.
The transition metal compounds as components (a-1) and component
(a-2) represented by the general formulae (I) and (II) respectively
include, for example, compounds described in Japanese Patent
Application No. 4-268308, Japanese Patent Application No. 5-306304,
Japanese Patent Application No. 6-100579, Japanese Patent
Application No. 6-157661, Japanese Patent Application No. 6-184179,
Japanese Patent Application No. 6-345809, Japanese Patent
Application No. 7-149815, Japanese Patent Application No. 7-188318,
Japanese Patent Application No. 7-258321 etc.
Specific examples include ethylene bis(indenyl) zirconium
dichloride, ethylene bis(2-methylindenyl) zirconium dichloride,
ethylene bis(tetrahydroindenyl) zirconium dichloride, ethylene
bis(2-methyltetrahydroindenyl) zirconium dichloride, 1,3-propylene
bis(indenyl) zirconium dichloride, 1,3-propylene
bis(2-methylindenyl) zirconium dichloride, 1,3-propylene
bis(tetrahydroindenyl) zirconium dichloride, 1,3-propylene
bis(2-methyltetrahydroindenyl) zirconium dichloride, 1,2-propylene
bis(indenyl) zirconium dichloride, 1,2-propylene
bis(2-methylindenyl) zirconium dichloride, 1,2-propylene
bis(tetrahydroindenyl) zirconium dichloride, 1,2-propylene
bis(2-methyltetrahydroindenyl) zirconium dichloride, 2,3-butylene
bis(indenyl) zirconium dichloride, 2,3-butylene
bis(2-methylindenyl) zirconium dichloride, 2,3-butylene
bis(tetrahydroindenyl) zirconium dichloride, 2,3-butylene
bis(2-methyltetrahydroindenyl) zirconium dichloride, dimethyl
silylene bis(indenyl) zirconium dichloride, dimethyl silylene
bis(2-methylindenyl) zirconium dichloride, dimethyl silylene
bis(2-methyl-4-methylindenyl) zirconium dichloride, dimethyl
silylene bis(2-methyl-4-ethylindenyl) zirconium dichloride,
dimethyl silylene bis(2-methyl-4-propylindenyl) zirconium
dichloride, dimethyl silylene bis(2-methyl-4-phenylindenyl)
zirconium dichloride, dimethyl silylene
bis(2-methyl-4-naphthylindenyl) zirconium dichloride, dimethyl
silylene bis(2-methyl-4-anthracenylindenyl) zirconium dichloride,
dimethyl silylene bis(2-methylbenz[e]indenyl) zirconium dichloride,
dimethyl silylene bis(2-methylbenz[f]indenyl) zirconium dichloride,
dimethyl silylene bis(2-ethylindenyl) zirconium dichloride,
dimethyl silylene bis(2-ethyl-4-phenylindenyl) zirconium
dichloride, dimethyl silylene bis(2-ethylbenz[e]indenyl) zirconium
dichloride, dimethylsilylene bis(2,5-dimethyl-4-methylindenyl)
zirconium dichloride, dimethyl silylene
bis(2,5-dimethyl-4-ethylindenyl) zirconium dichloride,
dimethylsilylene bis(2,5-dimethyl-4-propylindenyl) zirconium
dichloride, dimethyl silylene bis(2,5-dimethyl-4-phenylindenyl)
zirconium dichloride, dimethyl silylene
bis(2,5-dimethyl-4-naphthylindenyl) zirconium dichloride, dimethyl
silylene bis(2,5-dimethyl-4-anthracenylindenyl) zirconium
dichloride, dimethyl silylene bis(2,6-dimethyl-4-methylindenyl)
zirconium dichloride, dimethyl silylene
bis(2,6-dimethyl-4-ethylindenyl) zirconium dichloride, dimethyl
silylene bis(2,6-dimethyl-4-propylindenyl) zirconium dichloride,
dimethyl silylene bis(2,6-dimethyl-4-phenylindenyl) zirconium
dichloride, dimethyl silylene bis(2,6-dimethyl-4-naphthylindenyl)
zirconium dichloride, dimethyl silylene
bis(2,6-dimethyl-4-anthracenylindenyl) zirconium dichloride,
dimethyl silylene bis(2,7-dimethyl-4-methylindenyl) zirconium
dichloride, dimethyl silylene bis(2,7-dimethyl-4-ethylindenyl)
zirconium dichloride, dimethyl silylene
bis(2,7-dimethyl-4-propylindenyl) zirconium dichloride, dimethyl
silylene bis(2,7-dimethyl-4-phenylindenyl) zirconium dichloride,
dimethyl silylene bis(2,7-dimethyl-4-naphthylindenyl) zirconium
dichloride, dimethyl silylene
bis(2,7-dimethyl-4-anthracenylindenyl) zirconium dichloride,
phenylmethyl silylene bis(indenyl) zirconium dichloride,
phenylmethyl silylene bis(2-methylindenyl) zirconium dichloride,
phenylmethyl silylene bis(2-methyl-4-methylindenyl) zirconium
dichloride, phenylmethyl silylene bis(2-methyl-4-ethylindenyl)
zirconium dichloride, phenylmethyl silylene
bis(2-methyl-4-propylindenyl) zirconium dichloride, phenylmethyl
silylene bis(2-methyl-4-phenylindenyl) zirconium dichloride,
phenylmethyl silylene bis(2-methyl-4-naphthylindenyl) zirconium
dichloride, phenylmethyl silylene
bis(2-methyl-4-anthracenylindenyl) zirconium dichloride,
phenylmethyl silylene bis(2-methylbenz[e]indenyl) zirconium
dichloride, phenylmethyl silylene bis(2-methylbenz[f]indenyl)
zirconium dichloride, phenylmethyl silylene bis(2-ethylindenyl)
zirconium dichloride, phenylmethyl silylene
bis(2-ethyl-4-phenylindenyl) zirconium dichloride, phenylmethyl
silylene bis(2-ethylbenz[e]indenyl) zirconium dichloride,
phenylmethyl silylene bis(2,5-dimethyl-4-methylindenyl) zirconium
dichloride, phenylmethyl silylene bis(2,5-dimethyl-4-ethylindenyl)
zirconium dichloride, phenylmethyl silylene
bis(2,5-dimethyl-4-propylindenyl) zirconium dichloride,
phenylmethyl silylene bis(2,5-dimethyl-4-phenylindenyl) zirconium
dichloride, phenylmethyl silylene
bis(2,5-dimethyl-4-naphthylindenyl) zirconium dichloride,
phenylmethyl silylene bis(2,5-dimethyl-4-anthracenylindenyl)
zirconium dichloride, phenylmethyl silylene
bis(2,6-dimethyl-4-methylindenyl) zirconium dichloride,
phenylmethyl silylene bis(2,6-dimethyl-4-ethylindenyl) zirconium
dichloride, phenylmethyl silylene bis(2,6-dimethyl-4-propylindenyl)
zirconium dichloride, phenylmethyl silylene
bis(2,6-dimethyl-4-phenylindenyl) zirconium dichloride,
phenylmethyl silylene bis(2,6-dimethyl-4-naphthylindenyl) zirconium
dichloride, phenylmethyl silylene
bis(2,6-dimethyl-4-anthracenylindenyl) zirconium dichloride,
phenylmethyl silylene bis(2,7-dimethyl-4-methylindenyl) zirconium
dichloride, phenylmethyl silylene bis(2,7-dimethyl-4-ethylindenyl)
zirconium dichloride, phenylmethyl silylene
bis(2,7-dimethyl-4-propylindenyl) zirconium dichloride,
phenylmethyl silylene bis(2,7-dimethyl-4-phenylindenyl) zirconium
dichloride, phenylmethyl silylene
bis(2,7-dimethyl-4-naphthylindenyl) zirconium dichloride,
phenylmethyl silylene bis(2,7-dimethyl-4-anthracenylindenyl)
zirconium dichloride, and dibromide compounds, dialkyl compounds,
diaralkyl compounds, disilyl compounds, dialkoxy compounds, dithiol
compounds, disulfonic acid compounds, diamino compounds or
diphosphinic compounds of the above metallocene compounds, or
metallocene compounds wherein in the above compound, a central
metal is titanium or hafnium.
The component (a-3) is a transition metal compound represented by
the general formula (IV):
##STR00004## wherein R.sup.8 to R.sup.19 are independently selected
from a hydrogen atom, a halogen atom, a C1 to C20 alkyl group, a C3
to C20 cycloalkyl group, a C2 to C20 alkenyl group, a C6 to C20
aryl group and a C7 to C20 arylalkyl group, respectively, and can
contain a silicon, halogen or germanium atom, and adjacent
substituent groups out of R.sup.12 to R.sup.19may be bound to each
other to form a ring, R.sup.7 is a divalent group having two
ligands, and is a C1 to C20 hydrocarbon group, a C1 to C20
halogen-containing hydrocarbon group, a silicon-containing group or
a germanium- or tin-containing group, and two substituent groups on
the same carbon, silicon, germanium or tin atom may be bound to
each other to form a ring, t.sup.1 and t.sup.2independently
represent a group selected from a hydrogen atom, a halogen atom, a
C1 to C20 hydrocarbon group, a C1 to C20 halogen-containirig
hydrocarbon group, a silicon-containing group, an oxygen-containing
group, a sulfur-containing group, a nitrogen-containing group and a
phosphorus-containing group, respectively, and M is a transition
metal selected from titanium, zirconium and hafnium.
Among the groups represented by R.sup.8 to R.sup.19in the general
formula (IV), the halogen atom includes chlorine, bromine, fluorine
and iodine atoms; the C1 to C20 alkyl group includes, for example,
a methyl group, ethyl group, n-propyl group, isopropyl group,
n-butyl group, isobutyl group, s-butyl group, t-butyl group,
n-pentyl group, neopentyl group, n-hexyl group, octyl group, nonyl
group, dodecyl group, eicosyl group, norbornyl group, adamantyl
group etc.; the C3 to C20 cycloalkyl group includes a cyclopropyl
group, cyclobutyl group, cyclopentyl group, cyclohexyl group etc.;
the C2 to C20 alkenyl group includes a vinyl group, propenyl group,
cyclohexenyl group etc.; the C7 to C20 arylalkyl group includes
benzyl, phenylethyl, phenylpropyl etc.; and the C6 to C20 aryl
group includes phenyl, tolyl, dimethylphenyl, trimethylphenyl,
ethylphenyl, propylphenyl, biphenyl, .alpha.- or .beta.-naphthyl,
methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl,
acenaphthyl, phenarenyl, aceanthrenyl, tetrahydronaphthyl, indanyl,
biphenylyl etc. The halogen-containing group represented by R.sup.8
to R.sup.19 includes groups wherein in the above-mentioned alkyl
group, cycloalkyl group, alkenyl group, arylalkyl group and aryl
group, one or more hydrogen atoms were replaced by suitable halogen
atoms. The silicon- or germanium-containing group includes groups
wherein in the above-mentioned alkyl group, cycloalkyl group,
alkenyl group, arylalkyl group and aryl group, one or more carbon
atoms were replaced by silicon or germanium atoms. R.sup.8 to
R.sup.19may be the same or different from one another.
At least one adjacent pair out of R.sup.12 to R.sup.19on the
fluorene ring may be bound to each other to form a ring. The
fluorenyl group having formed such a ring includes, for example, a
benzofluorenyl group, dibenzofluorenyl group,
octahydrodibenzofluorenyl group,
octamethyloctahydrodibenzofluorenyl group etc. R.sup.7, t.sup.1 and
t.sup.2 each have the same meaning as defined in the general
formula (II) and (III), and can be exemplified by groups similar to
those described above.
Specific examples of the transition metal compound (a-3)
represented by the general formula (IV) include isopropylidene
(cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene
(cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium
dichloride, isopropylidene (cyclopentadienyl)
(3,6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene
(cyclopentadienyl) (octamethyloctahydridedibenzfluorenyl) zirconium
dichloride, diphenylmethylene (cyclopentadienyl) (fluotenyl)
zirconium dichloride, diphenylmethylene (cyclopentadienyl)
(2,7-di-tert-butylfluorenyl) zirconium dichloride,
diphenylmethylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl)
zirconium dichloride, diphenylmethylene (cyclopentadienyl)
(octamethyloctahydridedibenzfluorenyl) zirconium dichloride,
cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium
dichloride, cyclohexylidene (cyclopentadienyl)
(2,7-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene
(cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium
dichloride, cyclohexylidene (cyclopentadienyl)
(octamethyloctahydridedibenzfluorenyl) zirconium dichloride,
phenylmethylmethylene (cyclopentadienyl) (fluorenyl) zirconium
dichloride, phenylmethylmethylene (cyclopentadienyl)
(2,7-di-tert-butylfluorenyl) zirconium dichloride,
phenylmethylmethylene (cyclopentadienyl)
(3,6-di-tert-butylfluorenyl) zirconium dichloride,
phenylmethylmethylene (cyclopentadienyl)
(octamethyloctahydridedibenzfluorenyl) zirconium dichloride,
isopropylidene (3-tert-butylcyclopentadienyl) (fluorenyl),
zirconium dichloride, isopropylidene (3-tert-butylcyclopentadienyl)
(2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene
(3-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl)
zirconium dichloride, isopropylidene (3-tert-butylcyclopentadienyl)
(octamethyloctahydridedibenzfluorenyl) zirconium dichloride,
diphenylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl)
zirconium dichloride, diphenylmethylene
(3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl)
zirconium dichloride, diphenylmethylene
(3-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl)
zirconium dichloride, diphenylmethylene
(3-tert-butylcyclopentadienyl)
(octamethyloctahydridedibenzfluorenyl) zirconium dichloride,
cyclohexylidene (3-tert-butylcyclopentadienyl) (fluorenyl)
zirconium dichloride, cyclohexylidene
(3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl)
zirconium dichloride, cyclohexylidene
(3-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl)
zirconium dichloride, cyclohexylidene
(3-tert-butylcyclopentadienyl)
(octamethyloctahydridedibenzfluorenyl) zirconium dichloride,
phenylmethylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl)
zirconium dichloride, phenylmethylmethylene
(3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl)
zirconium dichloride, phenylmethylmethylene
(3-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl)
zirconium dichloride, phenylmethylmethylene
(3-tert-butylcyclopentadienyl)
(octamethyloctahydridedibenzfluorenyl) zirconium dichloride,
isopropylidene (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl)
zirconium dichloride, isopropylidene
(3-tert-butyl-5-methylcyclopentadienyl)
(2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene
(3-tert-butyl-5-methylcyclopentadienyl)
(3,6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene
(3-tert-butyl-5-methylcyclopentadienyl)
(octamethyloctahydridedibenzfluorenyl) zirconium dichloride,
diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl)
(fluorenyl) zirconium dichloride, diphenylmethylene
(3-tert-butyl-5-methylcyclopentadienyl)
(2,7-di-tert-butylfluorenyl) zirconium dichloride,
diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl)
(3,6-di-tert-butylfluorenyl) zirconium dichloride,
diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl)
(octamethyloctahydridedibenzfluorenyl) zirconium dichloride,
cyclohexylidene (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl)
zirconium dichloride, cyclohexylidene
(3-tert-butyl-5-methylcyclopentadienyl)
(2,7-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene
(3-tert-butyl-5-methylcyclopentadienyl)
(3,6-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene
(3-tert-butyl-5-methylcyclopentadienyl)
(octamethyloctahydride-dibenzfluorenyl) zirconium dichloride,
phenylmethylmethylene (3-tert-butyl-5-methylcyclopentadienyl)
(fluorenyl) zirconium dichloride, phenylmethylmethylene
(3-tert-butyl-5-methylcyclopentadienyl)
(2,7-di-tert-butylfluorenyl) zirconium dichloride,
phenylmethylmethylene (3-tert-butyl-5-methylcyclopentadienyl)
(3,6-di-tert-butylfluorenyl) zirconium dichloride,
phenylmethylmethylene (3-tert-butyl-5-methylcyclopentadienyl)
(octamethyloctahydridedibenzfluorenyl) zirconium dichloride, and
dibromide compounds, dialkyl compounds, diaralkyl compounds,
disilyl compounds, dialkoxy compounds, dithiol compounds,
disulfonic acid compounds, diamino compounds or diphosphinic
compounds of the above metallocene compounds, or metallocene
compounds wherein in the above compound, a central metal is
titanium or hafnium.
Among the transition metal compounds represented by the general
formulae (II), (III) and (IV), the transition metal compounds
represented by the general formulae (II) and (III) are preferable,
and the transition metal compounds represented by the general
formula (II) are particularly preferable.
The organoaluminum oxy compound (b) used in the present invention
(also referred to hereinafter as "component (b)") may be the
conventionally known aluminoxane, or may be a benzene-insoluble
organoaluminum oxy compound illustrated in Japanese Patent
Application No. 2-78687.
The conventionally known aluminoxane can be produced for example by
the following methods (i) to (iii): (i) A method in which an
organoaluminum compound such as trialkyl aluminum is added to and
reacted with a hydrocarbon suspension of a compound containing
adsorbed water or a salt containing water of crystallization, for
example magnesium chloride hydrate, copper sulfate hydrate,
aluminum sulfate hydrate, nickel sulfate hydrate or cerous chloride
hydrate. (ii) A method in which water, ice or water vapor is
allowed to act directly on an organoaluminum compound such as
trialkyl aluminum in a medium such as benzene, toluene, ethyl ether
or tetrahydrofuran. (iii) A method in which an organotin oxide such
as dimethyltin oxide or dibutyltin oxide is reacted with an
organoaluminum compound such as trialkyl aluminum in a medium such
as decane, benzene or toluene.
In the above methods, the aluminoxane is recovered as a hydrocarbon
solution. From the recovered solution of the aluminoxane, a solvent
or unreacted organoaluminum compound is removed by distillation,
and the resulting aluminoxane may be re-dissolved in a solvent.
Specifically, the organoaluminum compound used in preparing a
lumoxane includes trialkyl aluminumsuchas trimethyl aluminum,
triethyl aluminum, tripropyl aluminum, triisopropyl aluminum,
tri-n-butyl aluminum, triisobutyl aluminum, tri-s-butyl aluminum,
tri-t-butyl aluminum, tripentyl aluminum, trihexyl aluminum,
trioctyl aluminum, tridecyl aluminum etc.; tricycloalkyl aluminum
such as tricyclohexyl aluminum, tricyclooctyl aluminum etc.;
dialkyl aluminum halide such as dimethyl aluminum chloride, diethyl
aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum
chloride etc.; dialkyl aluminum hydride such as diethyl aluminum
hydride, diisobutyl aluminumhydride etc.; dialkyl aluminum alkoxide
such as dimethyl aluminum methoxide, diethyl aluminum ethoxide
etc.; and dialkyl aluminum aryloxide such as diethyl aluminum
phenoxide etc.
Among these compounds, trialkyl aluminum and tricycloalkyl aluminum
are particularly preferable. As the organoaluminum compound used in
preparing alumoxane, isoprenyl aluminum represented by the
following general formula (VI) can also be used.
(i--C.sub.4H.sub.9).sub.xAl.sub.y (C.sub.5H.sub.10).sub.z (VI)
wherein x, y and z each represents a positive number, and
z.gtoreq.2x.
The organoaluminum compounds described above are used singly or as
a mixture thereof. The solvent used in production of aluminoxane
includes aromatic hydrocarbons such as benzene, toluene, xylene,
cumene and cymene, aliphatic hydrocarbons such as pentane, hexane,
heptane, octane, decane, dodecane, hexadecane and octadecane,
alicyclic hydrocarbons such as cyclopentane, cyclohexane,
cyclooctane and methyl cyclopentane, petroleum fractions such as
gasoline, kerosene and light oil, or halogenated products of the
above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons and
alicyclic hydrocarbons, particularly chlorides and bromides
thereof. In addition, ethers such as ethyl ether, tetrahydrofuran
can also be used. Among these solvents, particularly the aromatic
hydrocarbons are preferable.
The benzene-insoluble organoaluminum oxy compound that can be used
in the present invention can be obtained by contacting a solution
of alumoxane with water or an active hydrogen-containing compound,
or by contacting the organoaluminum compound with water. In the
benzene-insoluble organoaluminum oxy compound, its Al component
dissolved in benzene at 60.degree. C. is 10% or less, preferably 5%
or less, more preferably 2% or less, in terms of Al atom, and the
organoaluminum oxy compound is insoluble or sparingly soluble in
benzene.
The above organoaluminum oxy compound (b) is usually commercially
available or handled as a toluene solution. The organoaluminum oxy
compound (b) used in the present invention may contain a small
amount of an organic compound component of metal other than
aluminum.
The (c) used in the present invention (also referred to hereinafter
as "component (c)") is a multifunctional organic halide represented
by the following general formula (I):
(Q.sup.1).sub.o--R--(Q.sup.2).sub.p (I) wherein R is a (o+p)
-valent group containing at least one halogen atom, o and p each
represent a positive integer satisfying the relationship
(o+p).gtoreq.2, Q.sup.1 and Q.sup.2 each represent--OH, --NH.sub.2
or --NLH whereupon L is an arbitrary group selected from a C1 to
C20 hydrocarbon group, a C1 to C20 halogen-containing hydrocarbon
group, a silicon-containing group, an oxygen-containing group, a
sulfur-containing group, a nitrogen-containing group and a
phosphorus-containing group, and L and R, N and R, or N and N may
be bound to each other to form a ring.
Among the groups represented by L in the substituent amino acid
group--NLH represented by Q.sup.1 and Q.sup.2 in the general
formula (I), the halogen atom includes chlorine, bromine, fluorine
and iodine atoms, and the C1 to C20 hydrocarbon group includes, for
example, an alkyl group such as methyl group, ethyl group, n-propyl
group, isopropyl group, n-butyl group, isobutyl group, t-butyl
group, n-hexyl group, n-decyl group etc., an aryl group such as
phenyl group, 1-naphthyl group, 2-naphthyl group etc., and an
aralkyl group such as benzyl group etc.
The C1 to C20 halogen-containing hydrocarbon group includes groups
(for example, a trifluoromethyl group) wherein in the
above-mentioned hydrocarbon group, one or more hydrogen atoms were
replaced by suitable hydrogen atoms. The silicon-containing group
includes a trimethyl silyl group, dimethyl (t-butyl) silyl group
etc., the oxygen-containing group includes a methoxy group, ethoxy
group etc., the sulfur-containing group includes a thiol group,
sulfonic acid group etc., the nitrogen-containing group includes a
dimethyl amino group etc., and the phosphorus-containing group
includes a phenyl phosphine group etc.
As specific examples of the multifunctional organic halide
represented by the above general formula (I), the OH--R--OH
compound [R has the same meaning as defined in the general formula
(I)] includes 3-fluorocatechol, 4-fluorocatechol,
3,4-difluorocatechol, 3,5-difluorocatechol, 3,6-difluorocatechol,
3,4,5-trifluorocatechol, 3,4,6-trifluorocatechol,
tetrafluorocatechol, 3-(trifluoromethyl) catechol,
4-(trifluoromethyl) catechol, 3,4-di(trifluoromethyl) catechol,
3,5-di(trifluoromethyl) catechol, 3,6-di(trifluoromethyl) catechol,
3,4,5-tri(trifluoromethyl) catechol, 3,4,6-tri(trifluoromethyl)
catechol, tetra(trifluoromethyl) catechol, 2-fluororesorcin,
4-fluororesorcin, 5-fluororesorcin, 2,4-difluororesorcin,
2,5-fluororesorcin, 4,5-difluororesorcin, 4,6-difluororesorcin,
5,6-difluororesorcin, 2,4,5-trifluororesorcin,
4,5,6-trifluororesorcin, tetrafluororesorcin, 2-(trifluoromethyl)
resorcin, 4-(trifluoromethyl) resorcin, 5-(trifluoromethyl)
resorcin, 2,4-di(trifluoromethyl) resorcin, 2,5-(trifluoromethyl)
resorcin, 4,5-di(trifluoromethyl) resorcin, 4,6-di(trifluoromethyl)
resorcin, 5,6-di(trifluoromethyl) resorcin,
2,4,5-tri(trifluoromethyl) resorcin, 4,5,6-tri(trifluoromethyl)
resorcin, tetra(trifluoromethyl) resorcin, 2-fluorohydroquinone,
3-fluorohydroquinone, 2,3-difluorohydroquinone,
2,5-difluorohydroquinone, 2,6-difluorohydroquinone,
2,3,5-trifluorohydroquinone, 2,3,6-trifluorohydroquinone,
tetrafluorohydroquinone, 2-(trifluoromethyl) hydroquinone,
3-(trifluoromethyl) hydroquinone, 2,3-di(trifluoromethyl)
hydroquinone, 2,5-di(trifluoromethyl) hydroquinone,
2,6-di(trifluoromethyl) hydroquinone, 2,3,5-tri(trifluoromethyl)
hydroquinone, 2,3,6-tri(trifluoromethyl) hydroquinone,
tetra(trifluoromethyl) hydroquinone,
1,3-bis(2-hydroxyhexafluoroisopropyl) benzene,
1,4-bis(2-hydroxyhexafluoroisopropyl) benzene,
2-fluoro-1,5-dihydroxy naphthalene, 3-fluoro-1,5-dihydroxy
naphthalene, 4-fluoro-1,5-dihydroxy naphthalene,
2,3-difluoro-1,5-dihydroxy naphthalene, 2,4-difluoro-1,5-dihydroxy
naphthalene, 2,6-difluoro-1,5-dihydroxy naphthalene,
2,7-difluoro-1,5-dihydroxy naphthalene, 2,8-difluoro-1,5-dihydroxy
naphthalene, 3,4-difluoro-1,5-dihydroxy naphthalene,
3,8-difluoro-1,5-dihydroxy naphthalene, 4,8-difluoro-1,5-dihydroxy
naphthalene, 2,3,4-trifluoro-1,5-dihydroxy naphthalene,
2,3,6-trifluoro-1,5-dihydroxy naphthalene,
2,3,7-trifluoro-1,5-dihydroxy naphthalene,
2,3,8-trifluoro-1,5-dihydroxy naphthalene,
2,3,6,7-tetrafluoro-1,5-dihydroxy naphthalene,
hexafluoro-1,5-dihydroxy naphthalene, 1-fluoro-2,6-dihydroxy
naphthalene, 3-fluoro-2,6-dihydroxy naphthalene,
4-fluoro-2,6-dihydroxy naphthalene, 1,3-difluoro-2,6-dihydroxy
naphthalene, 1,4-difluoro-2,6-dihydroxy naphthalene,
1,5-difluoro-2,6-dihydroxy naphthalene, 3,4-difluoro-2,6-dihydroxy
naphthalene, 3,5-difluoro-2,6-dihydroxy naphthalene,
4,5-difluoro-2,6-dihydroxy naphthalene,
1,3,4-trifluoro-2,6-dihydroxy naphthalene,
1,3,5-trifluoro-2,6-dihydroxy naphthalene,
3,4,5-trifluoro-2,6-dihydroxy naphthalene,
1,3,4,5-tetrafluoro-2,6-dihydroxy naphthalene,
hexafluoro-2,6-dihydroxy naphthalene, 2,3,4,5-tetrafluorobiphenol,
2,2',4,4'-tetrafluoro-4,4'-biphenol,
2,2',3,3',4,4',5,5',6,6'-octafluoro-4,4'-biphenol,
4,4'-bis(2-hydroxyhexafluoroisopropyl) diphenyl,
bis(2,3-difluoro-4-hydroxy) methane, bis(2,6-difluoro-4-hydroxy)
methane, bis(3,5-difluoro-4-hydroxy) methane,
bis(tetrafluoro-4-hydroxy) methane,
4,4'-bis(2-hydroxyhexafluoroisopropyl) diphenyl ether,
4,4'-isopropylidene bis(2,6-difluorophenol), tetrafluoroethylene
glycol, hexafluoro-1,3-propane glycol,
2,2,3,3'-tetrafluoro-1,4-butane diol, octafluoro-1,4-butane diol,
perfluoro-1,5-pentane diol, perfluoro-1,6-hexane diol,
perfluoro-1,7-heptane diol, perfluoro-1,8-octane diol, and
OH--R--OH compounds whose fluorine atom was replaced by a bromine
atom or a chlorine atom.
The H.sub.2N--R--NH.sub.2 compound [R has the same meaning as
defined in the general formula (I)] includes
2-amino-3-fluoroaniline, 2-amino-4-fluoroaniline,
2-amino-5-fluoroaniline, 2-amino-3,4-difluoroaniline,
2-amino-3,5-difluoroaniline, 2-amino-3,6-difluoroaniline,
2-amino-3,4,5-trifluoroaniline, 2-amino-3,4,6-trifluoroaniline,
2-amino-tetrafluoroaniline, 2-amino-3-(trifluoromethyl) aniline,
2-amino-4-(trifluoromethyl) aniline,
2-amino-3,4-di(trifluoromethyl) aniline,
2-amino-3,5-di(trifluoromethyl) aniline,
2-amino-3,6-di(trifluoromethyl) aniline,
2-amino-3,4,5-tri(trifluoromethyl) aniline,
2-amino-3,4,6-tri(trifluoromethyl) aniline,
2-amino-tetra(trifluoromethyl) aniline, 3-amino-2-fluoroaniline,
3-amino-4-fluoroaniline, 3-amino-5-fluoroaniline,
3-amino-2,4-difluoroaniline, 3-amino-2,5-fluoroaniline,
3-amino-4,5-difluoroaniline, 3-amino-4,6-difluoroaniline,
3-amino-5,6-difluoroaniline, 3-amino-2,4,5-trifluoroaniline,
3-amino-4,5,6-trifluoroaniline, 3-amino-tetrafluoroaniline,
3-amino-2-(trifluoromethyl) aniline, 3-amino-4-(trifluoromethyl)
aniline, 3-amino-5-(trifluoromethyl) aniline,
3-amino-2,4-di(trifluoromethyl) aniline,
3-amino-2,5-(trifluoromethyl) aniline,
3-amino-4,5-di(trifluoromethyl) aniline,
3-amino-4,6-di(trifluoromethyl) aniline,
3-amino-5,6-di(trifluoromethyl) aniline,
3-amino-2,4,5-tri(trifluoromethyl) aniline,
3-amino-4,5,6-tri(trifluoromethyl) aniline,
3-amino-tetra(trifluoromethyl) aniline, 4-amino-2-fluoroaniline,
4-amino-3-fluoroaniline, 4-amino-2,3-difluoroaniline,
4-amino-2,5-difluoroaniline, 4-amino-2,6-difluoroaniline,
4-amino-2,3,5-trifluoroaniline, 4-amino-2,3,6-trifluoroaniline,
4-amino-tetrafluoroaniline, 4-amino-2-(trifluoromethyl) aniline,
4-amino-3-(trifluoromethyl) aniline,
4-amino-2,3-di(trifluoromethyl) aniline,
4-amino-2,5-di(trifluoromethyl) aniline,
4-amino-2,6-di(trifluoromethyl) aniline,
4-amino-2,3,5-tri(trifluoromethyl) aniline,
4-amino-2,3,6-tri(trifluoromethyl) aniline,
4-amino-tetra(trifluoromethyl) aniline, 2-amino-6-fluorobenzyl
amine, 1,5-diamino-2-fluoronaphthalene,
1,5-diamino-3-fluoronaphthalene, 1,5-diamino-4-fluoronaphthalene,
1,5-diamino-2,3-difluoronaphthalene,
1,5-diamino-2,4-difluoronaphthalene,
1,5-diamino-2,6-difluoronaphthalene,
1,5-diamino-2,7-difluoronaphthalene,
1,5-diamino-2,8-difluoronaphthalene,
1,5-diamino-3,4-difluoronaphthalene,
1,5-diamino-3,8-difluoronaphthalene,
1,5-diamino-4,8-difluoronaphthalene,
1,5-diamino-2,3,4-trifluoronaphthalene,
1,5-diamino-2,3,6-trifluoronaphthalene,
1,5-diamino-2,3,7-trifluoronaphthalene,
1,5-diamino-2,3,8-trifluoronaphthalene,
1,5-diamino-2,3,6,7-tetrafluoronaphthalene,
1,5-diamino-hexafluoronaphthalene, 2,6-diamino-1-fluoronaphthalene,
2,6-diamino-3-fluoronaphthalene, 2,6-diamino-4-fluoronaphthalene,
2,6-diamino-1,3-difluoronaphthalene,
2,6-diamino-1,4-difluoronaphthalene,
2,6-diamino-1,5-difluoronaphthalene,
2,6-diamino-3,4-difluoronaphthalene,
2,6-diamino-3,5-difluoronaphthalene,
2,6-diamino-4,5-difluoronaphthalene,
2,6-diamino-1,3,4-trifluoronaphthalene,
2,6-diamino-1,3,5-trifluoronaphthalene,
2,6-diamino-3,4,5-trifluoronaphthalene,
2,6-diamino-1,3,4,5-tetrafluoronaphthalene,
2,6-diamino-hexafluoronaphthalene,
4-amino-4'-(N-methylamino)-2,3,4,5-tetrafluorobiphenyl,
4-amino-4'-(N-methylamino)-2,2',4,4'-tetrafluorobiphenyl,
4-amino-4'-(N-methylamino)-2,2',3,3',4,4',5,5',6,6'-octafluorobiphenyl,
2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl,
3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl,
4,4'-diaminooctafluorobiphenyl, bis(4-amino-2,3-difluorophenyl)
methane, bis(4-amino-2,6-difluorophenyl) methane,
bis(4-amino-3,5-difluorophenyl methane,
bis(4-amino-tetrafluorophenyl) methane,
2,2-bis(3-amino-4-methylphenyl) hexafluoropropane,
2,2-bis[4-(4-aminophenyl)]-hexafluoropropane,
2,2-bis(4-aminophenyl) hexafluoropropane,
4,4'-bis(2-amino-hexafluoroisopropyl) diphenyl ether,
4,4'-isopropylidene bis(2,6-difluoroaniline),
2,4-diamino-6-(4-fluorophenyl) pyrimidine,
2,4-diamino-5-fluoroquinazoline, 4,4'-diaminooctafluorobiphenyl,
tetrafluorosuccinamide, tetrafluoroethylene diamine,
hexafluoro-1,3-propene diamine, 2,2',3,3'-tetrafluoro-1,4-butylene
diamine, octafluoro-1,4-butylene diamine, decafluoro-1,5-pentene
diamine, perfluoro-1,6-hexene diamine, perfluoro-1,7-heptene
diamine, perfluoro-1,8-octene diamine, and H.sub.2N--R--NH.sub.2
compounds whose fluorine atom was replaced by a bromine atom or
chlorine atom.
The HLN--R--NLH compound [R and L have the same meaning as defined
in the general formula (I)] includes 3-fluoro-1,2-di(N-methylamino)
benzene, 4-fluoro-1,2-di(N-methylamino) benzene,
3,4-difluoro-1,2-di(N-methylamino) benzene,
3,5-difluoro-1,2-di(N-methylamino) benzene,
3,6-difluoro-1,2-di(N-methylamino) benzene,
3,4,5-trifluoro-1,2-di(N-methylamino) benzene,
3,4,6-trifluoro-1,2-di(N-methylamino) benzene,
tetrafluoro-1,2-di(N-methylamino) benzene,
2-fluoro-1,3-di(N-methylamino) benzene,
4-fluoro-1,3-di(N-methylamino) benzene,
5-fluoro-1,3-di(N-methylamino) benzene,
2,4-difluoro-1,3-di(N-methylamino) benzene,
2,5-fluoro-1,3-di(N-methylamino) benzene,
4,5-difluoro-1,3-di(N-methylamino) benzene,
4,6-difluoro-1,3-di(N-methylamino) benzene,
5,6-difluoro-1,3-di(N-methylamino) benzene,
2,4,5-trifluoro-1,3-di(N-methylamino) benzene,
4,5,6-trifluoro-1,3-di(N-methylamino) benzene,
tetrafluoro-1,3-di(N-methylamino) benzene,
2-fluoro-1,4-di(N-methylamino) benzene,
3-fluoro-1,4-di(N-methylamino) benzene,
2,3-difluoro-1,4-di(N-methylamino) benzene,
2,5-difluoro-1,4-di(N-methylamino) benzene,
2,6-difluoro-1,4-di(N-methylamino) benzene,
2,3,5-trifluoro-1,4-di(N-methylamino) benzene,
2,3,6-trifluoro-1,4-di(N-methylamino) benzene,
tetrafluoro-1,4-di(N-methylamino) benzene,
2-fluoro-1,5-di(N-methylamino) naphthalene,
3-fluoro-1,5-di(N-methylamino) naphthalene,
4-fluoro-1,5-di(N-methylamino) naphthalene,
2,3-difluoro-1,5-di(N-methylamino) naphthalene,
2,4-difluoro-1,5-di(N-methylamino) naphthalene,
2,6-difluoro-1,5-di(N-methylamino) naphthalene,
2,7-difluoro-1,5-di(N-methylamino) naphthalene,
2,8-difluoro-1,5-di(N-methylamino) naphthalene,
3,4-difluoro-1,5-di(N-methylamino) naphthalene,
3,8-difluoro-1,5-di(N-methylamino) naphthalene,
4,8-difluoro-1,5-di(N-methylamino) naphthalene,
2,3,4-trifluoro-1,5-di(N-methylamino) naphthalene,
2,3,6-trifluoro-1,5-di(N-methylamino) naphthalene,
2,3,7-trifluoro-1,5-di(N-methylamino) naphthalene,
2,3,8-trifluoro-1,5-di(N-methylamino) naphthalene,
2,3,6,7-tetrafluoro-1,5-di(N-methylamino) naphthalene,
hexafluoro-1,5-di(N-methylamino) naphthalene,
4,4'-di(N-methylamino)-2,3,4,5-tetrafluorobiphenyl,
4,4'-di(N-methylamino)-2,2',4,4'-tetrafluorobiphenyl,
4,4'-di(N-methylamino)-2,2',3,3',4,4',5,5',6,6'-octafluorobiphenyl,
bis(4-(N-methylamino)-2,3-difluorophenyl) methane,
bis((N-methylamino)-2,6-difluorophenyl) methane,
bis(4-(N-methylamino)-3,5-difluorophenyl) methane,
bis(4-(N-methylamino)-tetrafluorophenyl) methane,
4,4'-bis(2-(N-methylamino)-hexafluoroisopropyl) diphenyl ether,
tetrafluoroethylene diamine, hexafluoro-1,3-propene diamine,
2,2',3,3'-hexafluoro-1,4-butylene diamine, octafluoro-1,4-butylene
diamine, decafluoro-1,5-pentene diamine, perfluoro-1,6-hexene
diamine, perfluoro-1,7-heptene diamine, perfluoro-1,8-octene
diamine, 1,2-di(N-methylamino) tetrafluoroethane,
1,3-di(N-methylamino) hexafluoropropane,
1,4-di(N-methylamino)-2,2',3,3'-hexafluorobutane,
1,4-di(N-methylamino)-octafluorobutane,
1,5-di(N-methylamino)-decafluoropentane,
1,6-di(N-methylamino)-perfluorohexane,
1,7-di(N-methylamino)-perfluoropentane,
1,8-di(N-methylamino)-perfluooctane, 5-fluorouracil,
6-fluorouracil, 1-fluoroxanthine, 3-fluoroxanthine,
7-fluoroxanthine, 3-fluoroadenine, 5-fluoromethyl uracil,
5-trifluoromethyl uracil, 6-fluoromethyl uracil, 1-fluoromethyl
xanthine, 3-fluoromethyl xanthine, 7- fluoromethyl xanthine, 3-
fluoromethyl adenine, and HLN--R--NLH compounds whose fluorine atom
was replaced by a bromine atom or a chlorine atom.
The HO--R--NH.sub.2 compound [R has the same meaning as defined in
the general formula (I)] includes 2-amino-3-fluorophenol,
2-amino-4-fluorophenol, 2-amino-3,4-difluorophenol,
2-amino-3,5-difluorophenol, 2-amino-3,6-difluorophenol,
2-amino-3,4,5-trifluorophenol, 2-amino-3,4,6-trifluorophenol,
2-amino-tetrafluorophenol, 2-amino-3-(trifluoromethyl) phenol,
2-amino-4-(trifluoromethyl) phenol, 2-amino-3,4-di(trifluoromethyl)
phenol, 2-amino-3,5-di(trifluoromethyl) phenol,
2-amino-3,6-di(trifluoromethyl) phenol,
2-amino-3,4,5-tri(trifluoromethyl) phenol,
2-amino-3,4,6-tri(trifluoromethyl) phenol,
2-amino-tetra(trifluoromethyl) phenol, 3-amino-2-fluorophenol,
3-amino-4-fluorophenol, 3-amino-5-fluorophenol,
3-amino-2,4-difluorophenol, 3-amino-2,5-fluorophenol,
3-amino-4,5-difluorophenol, 3-amino-4,6-difluorophenol,
3-amino-5,6-difluorophenol, 3-amino-2,4,5-trifluorophenol,
3-amino-4,5,6-trifluorophenol, 3-amino-tetrafluorophenol,
3-amino-2-(trifluoromethyl) phenol, 3-amino-4-(trifluoromethyl)
phenol, 3-amino-5-(trifluoromethyl) phenol,
3-amino-2,4-di(trifluoromethyl) phenol,
3-amino-2,5-(trifluoromethyl) phenol,
3-amino-4,5-di(trifluoromethyl) phenol,
3-amino-4,6-di(trifluoromethyl) phenol,
3-amino-5,6-di(trifluoromethyl) phenol,
3-amino-2,4,5-tri(trifluoromethyl) phenol,
3-amino-4,5,6-tri(trifluoromethyl) phenol,
3-amino-tetra(trifluoromethyl) phenol, 4-amino-2-fluorophenol,
4-amino-3-fluorophenol, 4-amino-2,3-difluorophenol,
4-amino-2,5-difluorophenol, 4-amino-2,6-difluorophenol,
4-amino-2,3,5-trifluorophenol, 4-amino-2,3,6-trifluorophenol,
4-amino-tetrafluorophenol, 4-amino-2-(trifluoromethyl) phenol,
4-amino-3-(trifluoromethyl) phenol, 4-amino-2,3-di(trifluoromethyl)
phenol, 4-amino-2,5-di(trifluoromethyl) phenol,
4-amino-2,6-di(trifluoromethyl) phenol,
4-amino-2,3,5-tri(trifluoromethyl) phenol,
4-amino-2,3,6-tri(trifluoromethyl) phenol,
4-amino-tetra(trifluoromethyl) phenol, 5-amino-2-fluoro-1-hydroxy
naphthalene, 5-amino-3-fluoro-1-hydroxy naphthalene,
5-amino-4-fluoro-1-hydroxy naphthalene,
5-amino-2,3-difluoro-1-hydroxy naphthalene,
5-amino-2,4-difluoro-1-hydroxy naphthalene,
5-amino-2,6-difluoro-1-hydroxy naphthalene,
5-amino-2,7-difluoro-1-hydroxy naphthalene,
5-amino-2,8-difluoro-1-hydroxy naphthalene,
5-amino-3,4-difluoro-1-hydroxy naphthalene,
5-amino-3,8-difluoro-1-hydroxy naphthalene,
5-amino-4,8-difluoro-1-hydroxy naphthalene,
5-amino-2,3,4-trifluoro-1-hydroxy naphthalene,
5-amino-2,3,6-trifluoro-1-hydroxy naphthalene,
5-amino-2,3,7-trifluoro-1-hydroxy naphthalene,
5-amino-2,3,8-trifluoro-1-hydroxy naphthalene,
5-amino-2,3,6,7-tetrafluoro-1-hydroxy naphthalene,
5-amino-hexafluoro-1-hydroxy naphthalene,
2-amino-1-fluoro-6-hydroxy naphthalene, 2-amino-3-fluoro-6-hydroxy
naphthalene, 2-amino-4-fluoro-6-hydroxy naphthalene,
2-amino-1,3-difluoro-6-hydroxy naphthalene,
2-amino-1,4-difluoro-6-hydroxy naphthalene,
2-amino-1,5-difluoro-6-hydroxy naphthalene,
2-amino-3,4-difluoro-6-hydroxy naphthalene,
2-amino-3,5-difluoro-6-hydroxy naphthalene,
2-amino-4,5-difluoro-6-hydroxy naphthalene,
2-amino-1,3,4-trifluoro-6-hydroxy naphthalene,
2-amino-1,3,5-trifluoro-6-hydroxy naphthalene,
2-amino-3,4,5-trifluoro-6-hydroxy naphthalene,
2-amino-1,3,4,5-tetrafluoro-6-hydroxy naphthalene,
2-amino-hexafluoro-6-hydroxy naphthalene,
bis(4-amino-2,3-difluorophenyl) methane,
bis(4-amino-2,6-difluorophenyl) methane,
bis(4-hydroxy-3,5-difluorophenyl) methane,
bis(4-hydroxytetrafluorophenyl) methane,
4,4'-bis(2-amino-hexafluoroisopropyl) diphenyl ether,
4,4'-isopropylidene bis(2,6-difluoroaniline),
3,5-bis(trifluoromethyl) benzamide oxime,
5-(trifluoromethyl)pyridine-2-alboxyamide oxime,
2-amino-tetrafluoroethanol, 3-amino-hexafluoro-1-propanol,
4-amino-2,2',3,3'-tetrafluoro-1-butanol,
4-amino-octafluoro-1-butanol, 5-amino-perfluoro-1-pentanol,
6-amino-perfluoro-1-hexanol, 7-amino-perfluoro-1-heptanol,
8-amino-perfluoro-1-octanol, and HO--R--NH.sub.2 compounds whose
fluorine atom was replaced by a bromine atom or a chlorine
atom.
The HO--R--NLH compound [L and R have the same meaning as defined
in the general formula (I)] includes
2-(N-methylamino)-3-fluorophenol, 2-(N-methylamino)-4-fluorophenol,
2-(N-methylamino)-3,4-difluorophenol,
2-(N-methylamino)-3,5-difluorophenol,
2-(N-methylamino)-3,6-difluorophenol,
2-(N-methylamino)-3,4,5-trifluorophenol,
2-(N-methylamino)-3,4,6-trifluorophenol,
2-(N-methylamino)-tetrafluorophenol,
3-(N-methylamino)-2-fluorophenol, 3-(N-methylamino)-4-fluorophenol,
3-(N-methylamino)-5-fluorophenol,
3-(N-methylamino)-2,4-difluorophenol,
3-(N-methylamino)-2,5-fluorophenol,
3-(N-methylamino)-4,5-difluorophenol,
3-(N-methylamino)-4,6-difluorophenol,
3-(N-methylamino)-5,6-difluorophenol,
3-(N-methylamino)-2,4,5-trifluorophenol,
3-(N-methylamino)-4,5,6-trifluorophenol, 3-(N-methylamino)
tetrafluorophenol, 4-(N-methylamino)-2-fluorophenol,
4-(N-methylamino)-3-fluorophenol,
4-(N-methylamino)-2,3-difluorophenol,
4-(N-methylamino)-2,5-difluorophenol,
4-(N-methylamino)-2,6-difluorophenol,
4-(N-methylamino)-2,3,5-trifluorophenol,
4-(N-methylamino)-2,3,6-trifluorophenol, 4-(N-methylamino)
tetrafluorophenol, 5-(N-methylamino)-2-fluoro-1-hydroxy
naphthalene, 5-(N-methylamino)-3-fluoro-1-hydroxy naphthalene,
5-(N-methylamino)-4-fluoro-1-hydroxy naphthalene,
5-(N-methylamino)-2,3-difluoro-1-hydroxy naphthalene,
5-(N-methylamino)-2,4-difluoro-1-hydroxy naphthalene,
5-(N-methylamino)-2,6-difluoro-1-hydroxy naphthalene,
5-(N-methylamino)-2,7-difluoro-1-hydroxy naphthalene,
5-(N-methylamino)-2,8-difluoro-1-hydroxy naphthalene,
5-(N-methylamino)-3,4-difluoro-1-hydroxy naphthalene,
5-(N-methylamino)-3,8-difluoro-1-hydroxy naphthalene,
5-(N-methylamino)-4,8-difluoro-1-hydroxy naphthalene,
5-(N-methylamino)-2,3,4-trifluoro-1-hydroxy naphthalene,
5-(N-methylamino)-2,3,6-trifluoro-1-hydroxy naphthalene,
5-(N-methylamino)-2,3,7-trifluoro-1-hydroxy naphthalene,
5-(N-methylamino)-2,3,8-trifluoro-1-hydroxy naphthalene,
5-(N-methylamino)-2,3,6,7-tetrafluoro-1-hydroxy naphthalene,
5-(N-methylamino) hexafluoro-1-hydroxy naphthalene,
2-(N-methylamino)-1-fluoro-6-hydroxy naphthalene,
2-(N-methylamino)-3-fluoro-6-hydroxy naphthalene,
2-(N-methylamino)-4-fluoro-6-hydroxy naphthalene naphthalene,
2-(N-methylamino)-1,3-difluoro-6-hydroxy naphthalene,
2-(N-methylamino)-1,4-difluoro-6-hydroxy naphthalene,
2-(N-methylamino)-1,5-difluoro-6-hydroxy naphthalene,
2-(N-methylamino)-3,4-difluoro-6-hydroxy naphthalene,
2-(N-methylamino)-3,5-difluoro-6-hydroxy naphthalene,
2-(N-methylamino)-4,5-difluoro-6-hydroxy naphthalene,
2-(N-methylamino)-1,3,4-trifluoro-6-hydroxy naphthalene,
2-(N-methylamino)-1,3,5-trifluoro-6-hydroxy naphthalene,
2-(N-methylamino)-3,4,5-trifluoro-6-hydroxy naphthalene,
2-(N-methylamino)-1,3,4,5-tetrafluoro-6-hydroxy naphthalene,
2-(N-methylamino) hexafluoro-6-hydroxy naphthalene,
bis(4-(N-methylamino)-2,3-difluorophenyl) methane,
bis(4-(N-methylamino)-2,6-difluorophenyl) methane,
bis(4-hydroxy-3,5-difluorophenyl) methane,
bis(4-hydroxytetrafluorophenyl) methane, 4,4'-bis(2-(N-methylamino)
hexafluoroisopropyl) diphenyl ether, 4,4'-isopropylidene
bis(2,6-difluoroaniline), 2-(N-methylamino) tetrafluoroethanol,
3-(N-methylamino) hexafluoro-1-propanol,
4-(N-methylamino)-2,2',3,3'-tetrafluoro-1-butanol,
4-(N-methylamino) octafluoro-1-butanol, 5-(N-methylamino)
perfluoro-1-pentanol, 6-(N-methylamino) perfluoro-1-hexanol,
7-(N-methylamino) perfluoro-1-heptanol, 8-(N-methylamino)
perfluoro-1-octanol, 2-(N-trifluoromethylamino)-3-fluorophenol,
2-(N-trifluoromethylamino)-4-fluorophenol,
2-(N-trifluoromethylamino)-3,4-difluorophenol,
2-(N-trifluoromethylamino)-3,5-difluorophenol,
2-(N-trifluoromethylamino)-3,6-difluorophenol,
2-(N-trifluoromethylamino)-3,4,5-trifluorophenol,
2-(N-trifluoromethylamino)-3,4,6-trifluorophenol,
2-(N-trifluoromethylamino) tetrafluorophenol,
3-(N-trifluoromethylamino)-2-fluorophenol,
3-(N-trifluoromethylamino)-4-fluorophenol,
3-(N-trifluoromethylamino)-5-fluorophenol,
3-(N-trifluoromethylamino)-2,4-difluorophenol,
3-(N-trifluoromethylamino)-2,5-fluorophenol,
3-(N-trifluoromethylamino)-4,5-difluorophenol,
3-(N-trifluoromethylamino)-4,6-difluorophenol,
3-(N-trifluoromethylamino)-5,6-difluorophenol,
3-(N-trifluoromethylamino)-2,4,5-trifluorophenol,
3-(N-trifluoromethylamino)-4,5,6-trifluorophenol,
3-(N-trifluoromethylamino) tetrafluorophenol,
4-(N-trifluoromethylamino)-2-fluorophenol,
4-(N-trifluoromethylamino)-3-fluorophenol,
4-(N-trifluoromethylamino)-2,3-difluorophenol,
4-(N-trifluoromethylamino)-2,5-difluorophenol,
4-(N-trifluoromethylamino)-2,6-difluorophenol,
4-(N-trifluoromethylamino)-2,3,5-trifluorophenol,
4-(N-trifluoromethylamino)-2,3,6-trifluorophenol,
4-(N-trifluoromethylamino) tetrafluorophenol,
5-(N-trifluoromethylamino)-2-fluoro-1-hydroxy naphthalene,
5-(N-trifluoromethylamino)-3-fluoro-1-hydroxy naphthalene,
5-(N-trifluoromethylamino)-4-fluoro-1-hydroxy naphthalene,
5-(N-trifluoromethylamino)-2,3-difluoro-1-hydroxy naphthalene,
5-(N-trifluoromethylamino)-2,4-difluoro-1-hydroxy naphthalene,
5-(N-trifluoromethylamino)-2,6-difluoro-1-hydroxy naphthalene,
5-(N-trifluoromethylamino)-2,7-difluoro-1-hydroxy naphthalene,
5-(N-trifluoromethylamino)-2,8-difluoro-1-hydroxy naphthalene,
5-(N-trifluoromethylamino)-3,4-difluoro-1-hydroxy naphthalene,
5-(N-trifluoromethylamino)-3,8-difluoro-1-hydroxy naphthalene,
5-(N-trifluoromethylamino)-4,8-difluoro-1-hydroxy naphthalene,
5-(N-trifluoromethylamino)-2,3,4-trifluoro-1-hydroxy naphthalene,
5-(N-trifluoromethylamino)-2,3,6-trifluoro-1-hydroxy naphthalene,
5-(N-trifluoromethylamino)-2,3,7-trifluoro-1-hydroxy naphthalene,
5-(N-trifluoromethylamino)-2,3,8-trifluoro-1-hydroxy naphthalene,
5-(N-trifluoromethylamino)-2,3,6,7-tetrafluoro-1-hydroxy
naphthalene, 5-(N-trifluoromethylamino) hexafluoro-1-hydroxy
naphthalene, 2- (N-trifluoromethylamino)-1-fluoro-6-hydroxy
naphthalene, 2-(N-trifluoromethylamino)-3-fluoro-6-hydroxy
naphthalene, 2-(N-trifluoromethylamino)-4-fluoro-6-hydroxy
naphthalene, 2-(N-trifluoromethylamino)-1,3-difluoro-6-hydroxy
naphthalene, 2-(N-trifluoromethylamino)-1,4-difluoro-6-hydroxy
naphthalene, 2-(N-trifluoromethylamino)-1,5-difluoro-6-hydroxy
naphthalene, 2-(N-trifluoromethylamino)-3,4-difluoro-6-hydroxy
naphthalene, 2-(N-trifluoromethylamino)-3,5-difluoro-6-hydroxy
naphthalene, 2-(N-trifluoromethylamino)-4,5-difluoro-6-hydroxy
naphthalene, 2-(N-trifluoromethylamino)-1,3,4-trifluoro-6-hydroxy
naphthalene, 2-(N-trifluoromethylamino)-1,3,5-trifluoro-6-hydroxy
naphthalene, 2-(N-trifluoromethylamino)-3,4,5-trifluoro-6-hydroxy
naphthalene,
2-(N-trifluoromethylamino)-1,3,4,5-tetrafluoro-6-hydroxy
naphthalene, 2-(N-trifluoromethylamino) hexafluoro-6-hydroxy
naphthalene, bis(4-(N-trifluoromethylamino)-2,3-difluorophenyl)
methane, bis(4-(N-trifluoromethylamino)-2,6-difluorophenyl)
methane, bis(4-hydroxy-3,5-difluorophenyl) methane,
bis(4-hydroxytetrafluorophenyl) methane,
4,4-bis(2-(N-trifluoromethylamino) hexafluoroisopropyl) diphenyl
ether,4,4'-isopropylidene bis(2,6-difluoroaniline),
2-(N-trifluoromethylamino) tetrafluoroethanol,
3-(N-trifluoromethylamino) hexafluoro-1-propanol,
4-(N-trifluoromethylamino)-2,2',3,3'-tetrafluoro-1-butanol,
4-(N-trifluoromethylamino) octafluoro-1-butanol,
5-(N-trifluoromethylamino) perfluoro-1-pentanol,
6-(N-trifluoromethylamino) perfluoro-1-hexanol,
7-(N-trifluoromethylamino) perfluoro-1-heptanol,
8-(N-trifluoromethylamino) perfluoro-1-octanol, and HO--R--NLH
compounds whose fluorine atom was replaced by a bromine atom or
chlorine atom.
The H.sub.2N--R--NHL compound [L and R have the same meaning as
defined in the general formula (I)] includes
2-(N-methylamino)-3-fluoroaniline,
2-(N-methylamino)-4-fluoroaniline,
2-(N-methylamino)-3,4-difluoroaniline,
2-(N-methylamino)-3,5-difluoroaniline,
2-(N-methylamino)-3,6-difluoroaniline,
2-(N-methylamino)-3,4,5-trifluoroaniline,
2-(N-methylamino)-3,4,6-trifluoroaniline, 2-(N-methylamino)
tetrafluoroaniline, 3-(N-methylamino)-2-fluoroaniline,
3-(N-methylamino)-4-fluoroaniline,
3-(N-methylamino)-5-fluoroaniline,
3-(N-methylamino)-2,4-difluoroaniline,
3-(N-methylamino)-2,5-fluoroaniline,
3-(N-methylamino)-4,5-difluoroaniline,
3-(N-methylamino)-4,6-difluoroaniline,
3-(N-methylamino)-5,6-difluoroaniline,
3-(N-methylamino)-2,4,5-trifluoroaniline,
3-(N-methylamino)-4,5,6-trifluoroaniline, 3-(N-methylamino)
tetrafluoroaniline, 4-(N-methylamino)-2-fluoroaniline,
4-(N-methylamino)-3-fluoroaniline,
4-(N-methylamino)-2,3-difluoroaniline,
4-(N-methylamino)-2,5-difluoroaniline,
4-(N-methylamino)-2,6-difluoroaniline,
4-(N-methylamino)-2,3,5-trifluoroaniline,
4-(N-methylamino)-2,3,6-trifluoroaniline, 4-(N-methylamino)
tetrafluoroaniline, 5-amino-2-fluoro-1-(N-methylamino) naphthalene,
5-amino-3-fluoro-1-(N-methylamino) naphthalene,
5-amino-4-fluoro-1-(N-methylamino) naphthalene,
5-amino-2,3-difluoro-1-(N-methylamino) naphthalene,
5-amino-2,4-difluoro-1-(N-methylamino) naphthalene,
5-amino-2,6-difluoro-1-(N-methylamino) naphthalene,
5-amino-2,7-difluoro-1-(N-methylamino) naphthalene,
5-amino-2,8-difluoro-1-(N-methylamino) naphthalene,
5-amino-3,4-difluoro-1-(N-methylamino) naphthalene,
5-amino-3,8-difluoro-1-(N-methylamino) naphthalene,
5-amino-4,8-difluoro-1-(N-methylamino) naphthalene,
5-amino-2,3,4-trifluoro-1-(N-methylamino) naphthalene,
5-amino-2,3,6-trifluoro-1-(N-methylamino) naphthalene,
5-amino-2,3,7-trifluoro-1-(N-methylamino) naphthalene,
5-amino-2,3,8-trifluoro-1-(N-methylamino) naphthalene,
5-amino-2,3,6,7-tetrafluoro-1-(N-methylamino) naphthalene,
5-amino-hexafluoro-1-(N-methylamino) naphthalene,
2-amino-1-fluoro-6-(N-methylamino) naphthalene,
2-amino-3-fluoro-6-(N-methylamino) naphthalene,
2-amino-4-fluoro-6-(N-tnethylamino) naphthalene naphthalene,
2-amino-1,3-difluoro-6-(N-methylamino) naphthalene,
2-amino-1,4-difluoro-6-(N-methylamino) naphthalene,
2-amino-1,5-difluoro-6-(N-methylamino) naphthalene,
2-amino-3,4-difluoro-6-(N-methylamino) naphthalene,
2-amino-3,5-difluoro-6-(N-methylamino) naphthalene,
2-amino-4,5-difluoro-6-(N-methylamino) naphthalene,
2-amino-1,3,4-trifluoro-6-(N-methylamino) naphthalene,
2-amino-1,3,5-trifluoro-6-(N-methylamino) naphthalene,
2-amino-3,4,5-trifluoro-6-(N-methylamino) naphthalene,
2-amino-1,3,4,5-tetrafluoro-6-(N-methylamino) naphthalene,
2-amino-hexafluoro-6-(N-methylamino) naphthalene,
4-amino-4'-(N-methylamino)-2,3,4,5-tetrafluorobiphenyl,
4-amino-4'-(N-methylamino)-2,2',4,4'-tetrafluorobiphenyl,
4-amino-4'-(N-methylamino)-2,2',3,3',4,4',5,5',6,6'-octafluorobiphenyl,
(4-amino-2,3-difluorophenyl)
(4-(N-methylamino)-2,3-difluorobiphenyl) methane,
(4-amino-2,6-difluorophenyl) (4-(N-methylamino)-2,6-difluorophenyl)
methane, (4-amino-3,5-difluorophenyl)
(4-(N-methylamino)-3,5-difluorophenyl) methane,
(4-amino-tetrafluorophenyl) (4-(N-methylamino)-tetrafluorophenyl)
methane, (4-(2-amino-hexafluoroisopropyl))
(4-(4-(N-methylamino)-hexafluoroisopropyl)) diphenyl ether,
1-amino-2-(N-methylamino) tetrafluoroethane,
1-amino-3-(N-methylamino)-hexafluoropropane,
1-amino-4-(N-methylamino)-2,2',3,3'-hexafluorobutane,
1-amino-4-(N-methylamino)-octafluorobutane,
1-amino-5-(N-methylamino)-decafluoropentane,
1-amino-6-(N-methylamino)-perfluorohexane,
1-amino-7-(N-methylamino)-perfluoropentane,
1-amino-8-(N-methylamino)-perfluorooctane,
(4-bromotetrafluorophenyl) hydrazine, 2-chloro-6-fluorophenyl
hydrazine, 3-chloro-4-fluorophenyl hydrazine,
2-chloro-4-(trifluoromethyl) phenyl hydrazine,
2-chloro-5-trifluoromethyl phenyl hydrazine,
2,4-dictoto-6-(trifluoromethyl) phenyl hydrazine,
2,6-dictoto-6-(trifluoromethyl) phenyl hydrazine, 2,4-fluorophenyl
hydrazine, 2,5-fluorophenyl hydrazine, 5-fluoro-2-methylphenyl
hydrazine, 4-fluorophenyl hydrazine, pentafluorophenyl hydrazine,
4-(trifluoromethoxy) phenyl hydrazine, 2-(trifluoromethyl) phenyl
hydrazine, 2-amino-6-fluoro-purine,
2-amino-6-trifluoromethyl-purine, and H.sub.2N--R--NLH compounds
whose fluorine atom was replaced by a bromine atom or chlorine
atom.
Preferable among those described above are tetrafluororesorcin,
tetrafluorohydroquinone, tetrabromohydroquinone,
1,4-bis(2-hydroxyhexafluoroisopropyl) benzene,
4,4'-bis(2-hydroxyhexafluoroisopropyl) diphenyl,
4,4'-bis(2-hydroxyhexafluoroisopropyl) diphenyl ether,
2,2',3,3'-tetrafluoro-1,4-butane diol, 2-amino-5-fluoroaniline,
2-amino-6-fluorobenzyl amine,
2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl,
3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl,
4,40-diaminooctafluorobiphenyl, 2,2-bis(3-amino-4-methylphenyl)
hexafluoropropane, 2,2-bis[4-(4-methylphenyl)]-hexafluoropropane,
2,2-bis(4-aminophenyl) hexafluoropropane,
4,40-diaminooctafluorobiphenyl, 5-trifluoromethyl uracil and
4-amino-3-fluorophenol, particularly preferably
tetrafluororesorcin, tetrafluorohydroquinone,
tetrabromohydroquinone, 4,4'-diaminooctafluorobiphenyl, and
2,2',3,3'-tetrafluoro-1,4-butane diol.
The organoaluminum compound (d) used if necessary in the present
invention (also referred to hereinafter as "component (d)") can be
exemplified by organoaluminum compounds represented by, for
example, the following general formula (VII):
R.sup.a.sub.nAlT.sub.3-n (VII) wherein R.sup.a represents a C1 to
C12 hydrocarbon group, T represents a halogen atom or a hydrogen
atom, and n is 1 to 3.
In the general formula (VII), R.sup.a is a hydrocarbon group having
1 to 12 carbon atoms, for example an alkyl group, cycloalkyl group
or aryl group, specifically a methyl group, ethyl group, n-propyl
group, isopropyl group, n-butyl group, isobutyl group, pentyl
group, hexyl group, isohexyl group, heptyl group, nonyl group,
octyl group, cyclopentyl group, cyclohexyl group, phenyl group and
tolyl group. Specifically, the organoaluminum compound (d) includes
trialkyl aluminum such as trimethyl aluminum, triethyl aluminum,
triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum,
tri-2-ethylhexyl aluminum etc.; alkenyl aluminum such as isoprenyl
aluminum etc.; dialkyl aluminum halide such as dimethyl aluminum
chloride, diethyl aluminum chloride, diisopropyl aluminum chloride,
diisobutyl aluminum chloride, dimethyl aluminum bromide etc.; alkyl
aluminum sesquihalide such as methyl aluminum sesquichloride, ethyl
aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl
aluminum sesquichloride, ethyl aluminum sesquibromide etc.; alkyl
aluminum dihalide such as methyl aluminum dichloride, ethyl
aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum
dibromide etc.; and alkyl aluminum hydride such as dimethyl
aluminum hydride, diethyl aluminum hydride, dihydrophenyl aluminum,
diisopropyl aluminum hydride, di-n-butyl aluminum hydride,
diisobutyl aluminum hydride, diisohexyl aluminum hydride, diphenyl
aluminum hydride, dicyclohexyl aluminum hydride, di-sec-heptyl
aluminum hydride, di-sec-nonyl aluminum hydride etc.
As the organoaluminum compound (d), compounds represented by the
following general formula (VIII) can also be used.
R.sup.a.sub.nAlU.sub.3-n (VIII) wherein R.sup.a has the same
meaning as defined above, U is --OR.sup.b group, --OSiR.sup.c.sub.3
group, --OAlR.sup.d.sub.2 group, --NR.sup.2.sub.2 group,
--SiR.sup.f.sub.3 group or --N(R.sup.g)AlR.sup.h.sub.2 group, n is
1 to 2, R.sup.b, R.sup.c, R.sup.d and R.sup.h are each a methyl
group, ethyl group, isopropyl group, isobutyl group, cyclohexyl
group, phenyl group or the like, R.sup.e is a hydrogen atom, methyl
group, ethyl group, isopropyl group, phenyl group, trimethyl silyl
group or the like, and R.sup.f and R.sup.g are each a methyl group,
ethyl group or the like.
As the organoaluminum compound, the following compounds are
specifically used.
(1) Compounds represented by R.sup.a.sub.nAl (OR.sup.b).sub.3-n,
for example, dimethyl aluminum methoxide, diethyl aluminum
ethoxide, diisobutyl aluminum methoxide etc., (2) compounds
represented by R.sup.a.sub.nAl(OSiR.sup.c.sub.3).sub.3-n, for
example, Et.sub.2Al(OSiMe.sub.3), (iso-Bu).sub.2Al (OSiMe.sub.3),
(iso-Bu).sub.2Al(OSiEt.sub.3) etc., (3) compounds represented by
R.sup.a.sub.nAl(OAlR.sup.d.sub.2).sub.3-n, for example,
Et.sub.2AlOAlEt.sub.2, (iso-Bu).sub.2AlOAl(iso-Bu).sub.2 etc., (4)
compounds represented by R.sup.a.sub.nAl(NR.sup.e).sub.3-n, for
example, Me.sub.2AlNEt.sub.2, Et.sub.2AlNHMe, Me.sub.2AlNHEt,
Et.sub.2AlN(SiMe.sub.3).sub.2, (iso-Bu).sub.2AlN(SiMe.sub.3).sub.2
etc., (5) compounds represented by
R.sup.a.sub.nAl(SiR.sup.f.sub.3).sub.3-n, for example,
(iso-Bu).sub.2AlSiMe.sub.3 etc., and (6) compounds represented by
R.sup.a.sub.nAl[N(R.sup.g) --AlR.sup.h.sub.2].sub.3-n, for example,
Et.sub.2AlN(Me)AlEt.sub.2, (iso-Bu).sub.2AlN(Et)Al(iso-Bu).sub.2
etc.
The organoaluminum compounds represented by the general formulae
(VII) and (VIII) are preferably compounds represented by the
general formula R.sup.a.sub.3Al wherein R.sup.a is preferably a C1
to C4 alkyl group.
The above components in the olefin polymerization catalyst
according to the present invention are carried on the following
solid carrier. As the solid carrier used in the present invention,
granular or fine particle solids made of an inorganic or organic
compound having a particle diameter of 3 to 300 .mu.m, preferably 5
to 200 .mu.m, are used. The inorganic carrier is preferably a
porous oxide, and can be specifically exemplified by SiO.sub.2,
Al.sub.2O.sub.3, MgO, ZrO.sub.2, TiO.sub.2, B.sub.2O.sub.3, CaO,
ZnO, BaO and ThO.sub.2 or mixtures containing them, for example
SiO.sub.2--MgO, SiO.sub.2--Al.sub.2O.sub.3, SiO.sub.2--TiO.sub.2,
SiO.sub.2--V.sub.2O.sub.5, SiO.sub.2--Cr.sub.2O.sub.3 and
SiO.sub.2--TiO.sub.2--MgO. Preferable among these carriers is a
carrier based on at least one member selected from the group
consisting of SiO.sub.2 and Al.sub.2O.sub.3. The above inorganic
oxide may contain a small amount of carbonates, sulfates, nitrates
and oxide components such as Na.sub.2CO.sub.3, K.sub.2CO.sub.3,
CaCO.sub.3, MgCO.sub.3, Na.sub.2SO.sub.4, Al.sub.2(SO.sub.4).sub.3,
BaSO.sub.4, KNO.sub.3, Mg(NO.sub.3).sub.2, Al(NO.sub.3).sub.3,
Na.sub.2O, K.sub.2O, Li.sub.2O
Although the properties of such solid carriers are varied depending
on the type and process thereof, the specific surface area of the
solid carrier used preferably in the present invention is 50 to
1000 m.sup.2/g, preferably 100 to 800 m.sup.2/g, and the porosity
thereof is desirably 0.3 to 2.5 cm.sup.3/g. The solid carrier is
used if necessary after baking at a temperature of 100 to
1000.degree. C., preferably 150 to 700.degree. C.
Although the properties of such solid carriers are varied depending
on the type and process thereof, the specific surface area of the
solid carrier used preferably in the present invention is 50 to
1000 m.sup.2/g, preferably 100 to 700 m.sup.2/g, and the porosity
thereof is desirably 0.3 to 2.5 cm.sup.3/g. The solid carrier is
used if necessary after baking at a temperature of 100 to
1000.degree. C., preferably 150 to 700.degree. C.
The solid carrier which can be used in the present invention
includes granular or fine particle solids made of an organic
compound having a particle diameter of 3 to 300 .mu.m. The organic
compound can be exemplified by (co)polymers formed from C2 to C14
.alpha.-olefins such as ethylene, propylene, 1-butene,
4-methyl-1-pentene etc. as the main component or by polymers or
copolymers formed from vinyl cyclohexane and styrene as the main
component.
Now, the olefin polymerization solid catalyst of the present
invention is described in more detail. The first olefin
polymerization solid catalyst of the present invention
comprises:
a solid carrier,
(A) a solid transition metal catalyst component obtained by
contacting (a) a compound of a transition metal of the group 4 in
the periodic table, containing at least one ligand having a
cyclopentadienyl skeleton, (b) an organoaluminum oxy compound, and
(c) a multifunctional organic halide represented by the following
general formula (I): (Q.sup.1).sub.o--R--(Q.sup.2).sub.p (I)
wherein R is a (o+p)-valent group containing at least one halogen
atom, o and p each represent a positive integer satisfying the
relationship (o+p).gtoreq.2, Q.sup.1 and Q.sup.2 each represent
--OH, --NH.sub.2 or --NLH whereupon L is an arbitrary group
selected from a C1 to C20 hydrocarbon group, a C1 to C20
halogen-containing hydrocarbon group, a silicon-containing group,
an oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group and a phosphorus-containing group, and L
and R, N and R, or N and N may be bound to each other to form a
ring, and
(B) an organoaluminum compound.
The solid transition metal catalyst component (A) can be prepared
by mixing and contacting the components (a), (b) and (c) and the
solid carrier with each other in an inert hydrocarbon.
The order of mixing these components is arbitrary, but it is
desirable that the components (a) and (c) are not directly mixed
and contacted with each other. Such direct contact may cause
decomposition and deterioration of the component (a), and it is
highly possible that the catalytic activity of the finally obtained
olefin polymerization catalyst is significantly deteriorated.
The preferable contact order includes, for example: i) a method
wherein component (b) is mixed and contacted with the solid
carrier, then component (a) is contacted therewith, and then
component (c) is contacted therewith, ii) a method wherein
component (b) is mixed and contacted with the solid carrier, then
component (c) is contacted therewith, and then component (a) is
contacted therewith, iii) a method wherein components (a) and (b)
are mixed and contacted with each other, and then the solid carrier
and then component (c) are mixed and contacted therewith, iv) a
method wherein the solid carrier is contacted with a contacted
mixture of components (b) and (c), and then component (a) is mixed
and contacted therewith, v) a method wherein component (b) is mixed
and contacted with the solid carrier, then component (a) is
contacted therewith, then component (c) is contacted therewith, and
component (b) is contacted again therewith, vi) a method wherein
component (b) is mixed and contacted with the solid carrier, then
component (c) is contacted therewith, then component (b) is
contacted again therewith, and further component (a) is contacted
therewith, and vii) a method wherein components (a) and (b) are
first mixed and contacted with each other, then the solid carrier,
then component (c) and further again component (b) are mixed and
contacted therewith.
The second olefin polymerization catalyst (C-2) according to the
present invention comprises: a solid carrier; (A) a solid
transition metal catalyst component obtained by contacting (a) a
compound of a transition metal of the group 4 in the periodic
table, containing at least one ligand having a cyclopentadienyl
skeleton, (b) an organoaluminum oxy compound, (c) a multifunctional
organic halide represented by the general formula (I), and (d) an
organoaluminum compound, and (B) an organoaluminum compound.
The solid transition metal catalyst component (A) can be prepared
by mixing and contacting the components (a), (b), (c) and (d) and
the solid carrier with each other in an inert hydrocarbon.
The order of mixing these components is arbitrary, but for the same
reason as described above, it is desirable that the components (a)
and (c) are not directly mixed and contacted with each other.
The preferable contact order includes, for example: i) a method
wherein component (b) is mixed and contacted with the solid
carrier, then component (a) is contacted therewith, and then
components (c) and (d), or a contacted mixture of components (c)
and (d), is contacted therewith, ii) a method wherein component (b)
is mixed and contacted with the solid carrier, then component (c)
is contacted therewith, and then component (a) or (d) is contacted
therewith, iii) a method wherein components (a) and (b) are first
mixed and contacted with each other, and then the solid carrier and
then components (c) and (d) or a contacted mixture of components
(c) and (d) are mixed and contacted therewith, and iv) a method
wherein the solid carrier is contacted with a contacted mixture of
components (b) and (c), and then component (a) or (d) is mixed and
contacted therewith.
The organoaluminum compound (B) used if necessary in the present
invention (also referred to hereinafter as "component (B)") can be
exemplified by the same organoaluminum compounds as for component
(d), among which the organoaluminum compounds represented by the
general formulae R.sup.a.sub.3Al, R.sup.a.sub.nAl
(OR.sup.b).sub.3-n, and R.sup.a.sub.nAl (OAlR.sup.d.sub.2).sub.3-n
are preferable wherein R.sup.a is preferably an isoalkyl group and
n is preferably 2.
In the present invention, in mixing the respective components the
component (a) is used in an amount of 10.sup.-6 to
5.times.10.sup.-4 mole, preferably 5.times.10.sup.-6 to
2.times.10.sup.-4 mole, per g of the solid carrier, and the
concentration of the component (a) is in the range of 10.sup.-5 to
10.sup.-2 mole/L in the solvent, preferably 5.times.10.sup.-5 to
5.times.10.sup.-3 mole/L in the solvent. The component (b) is used
in an amount of 10 to 1000, preferably 50 to 500, in terms of the
atomic ratio (Al/transition metal) of aluminum (Al) derived from
the component (b) to the transition metal derived from the
component (a). The component (c) is used in an amount of 0.01 to
5.0 moles, preferably 0.02 to 1.0 mole, more preferably 0.03 to 0.5
mole, per mole of aluminum derived from the component (b). When the
component (d) is used, the component (d) is used such that the gram
atomic ratio (Al-d/Al-b) of the aluminum atom (Al-d) in the
component (d) to the aluminum atom (Al-b) in the component (b)
becomes 0.01 to 2.0, preferably 0.02 to 1.0.
The mixing temperature in mixing the respective components is -50
to 150.degree. C., preferably -20 to 120.degree. C., and the
contacting time is 1 to 1000 minutes, preferably 5 to 600 minutes.
During mixing and contacting, the mixing temperature may be
changed.
In a preferable contacting mode of the present invention, there is
a method wherein components (b) and (c) are previously mixed and
contacted with each other in an inert hydrocarbon to prepare a
solution containing the components (b) and (c) mixed and contacted
therein, and then the solution is mixed and contacted with the
other components. When the components (b) and (c) are to be mixed
and contacted with each other, the concentration of component (b)
is 0.01 to 5 moles/L in the solvent, preferably 0.1 to 3 moles/L in
the solvent. The amount of component (c) is desirably 0.01 to 5.0
moles, preferably 0.02 to 1.0 mole, more preferably 0.03 to 0.5
mole, per mole of aluminum derived from the component (b). The
mixing temperature in mixing and contacting the components (b) and
(c) is -90.degree. C. to 150.degree. C., preferably -80.degree. C.
to 120.degree. C., and the contacting time is 1 to 1000 minutes,
preferably 5 to 600 minutes.
Specific examples of the inert hydrocarbon used in preparing the
catalyst in the present invention include aliphatic hydrocarbons
such as propane, butane, pentane, hexane, heptane, octane, decane,
dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane,
cyclohexane and methylcyclopentane; aromatic hydrocarbons such as
benzene, toluene and xylene; halogenated hydrocarbons such as
ethylene chloride, chlorobenzene and dichloromethane, or mixtures
thereof.
In the first olefin polymerization catalyst (C-1) according to the
present invention, it is preferable that per g of the solid
carrier, the transition metal atom derived from the component (a)
is carried in an amount of 10.sup.-4 to 5.times.10.sup.-2 gram
atom, preferably 5.0.times.10.sup.-4 to 2.times.10.sup.-2 gram
atom, the aluminum atom derived from the component (b) is carried
in an amount of 10.sup.-4 to 1.0 gram atom, preferably
5.times.10.sup.-3 to 5.times.10.sup.-1 gram atom, and the component
(c) is carried in an amount of 5.times.10.sup.-5 to
5.times.10.sup.-2 mole, desirably 10.sup.-5 to 10.sup.-2 mole. The
component (B) used if necessary is used desirably in an amount of
500 moles or less, preferably 1 to 200 moles, per gram atom of the
transition metal atom derived from the component (a).
In the second olefin polymerization catalyst (C-2) according to the
present invention, it is preferable that per g of the solid
carrier, the transition metal atom derived from the component (a)
is carried in an amount of 5.times.10.sup.-5 to 5.times.10.sup.-2
gram atom, preferably 10.sup.-5 to 10.sup.-2 gram atom, the
aluminum atom derived from the components (b) and (d) is carried in
an amount of 10.sup.-3 to 1.0 gram atom, preferably
5.0.times.10.sup.-3 to 5.times.10.sup.-1 gram atom, and the
component (c) is carried in an amount of 5.times.10.sup.-5 to
5.times.10.sup.-2 mole, desirably 10.sup.-5 to 10.sup.-2 mole. The
component (B) used if necessary is used desirably in an amount of
500 moles or less, preferably 1 to 200 moles, per gram atom of the
transition metal atom derived from the component (a).
The first and second olefin polymerization catalysts (C-1) and
(C-2) can be used as such, or may be used after the olefin
polymerization catalyst may be pre-polymerized with an olefin to
form a pre-polymerized catalyst. The pre-polymerization will be
described later in detail.
The third olefin polymerization catalyst (C-3) according to the
present invention is characterized in that a polymer having a
Z-average molecular weight of 6,000,000 or more by gel permeation
chromatography and having a die-swell ratio of 1.4 or more,
obtained by contacting ethylene, or ethylene and a C4 to C10
.alpha.-olefin, with a catalyst comprising a solid carrier, (A) a
solid transition metal catalyst component obtained by contacting
(a) a compound of a transition metal of the group 4 in the periodic
table, containing at least one ligand having a cyclopentadienyl
skeleton, (b) an organoaluminum oxy compound, and (c) a
multifunctional organic halide represented by the general formula
(I), and if necessary (B) an organoaluminum compound, wherein 0.01
to 1000 g of the polymer is pre-polymerized per g of the solid
transition metal catalyst component.
The solid transition metal catalyst component used in the present
invention can be prepared by mixing and contacting the components
(a), (b) and (c) and the solid carrier with each other in an inert
hydrocarbon. The order of mixing these components is arbitrary, but
it is desirable that the components (a) and (c) are not directly
mixed and contacted with each other. Such direct contact may cause
decomposition and deterioration of the component (a), and it is
highly possible that the catalytic activity of the finally obtained
olefin polymerization catalyst is significantly deteriorated. The
preferable contact order includes, for example: (i) a method
wherein component (b) is mixed and contacted with the solid
carrier, then component (a) is contacted therewith, and then
component (c) is contacted therewith, (ii) a method wherein
component (b) is mixed and contacted with the solid carrier, then
component (c) is contacted therewith, and then component (a) is
contacted therewith, (iii) a method wherein components (a) and (b)
are first mixed and contacted with each other, and then the solid
carrier and then component (c) are mixed and contacted therewith,
(iv) a method wherein the solid carrier is contacted with a
contacted mixture of components (b) and (c), and then component (a)
is mixed and contacted therewith, (v) a method wherein component
(b) is mixed and contacted with the solid carrier, then component
(a) is contacted therewith, then component (c) is contacted
therewith, and component (b) is contacted again therewith, (vi) a
method wherein component (b) is mixed and contacted with the solid
carrier, then component (c) is contacted therewith, then component
(b) is contacted again therewith, and further component (a) is
contacted therewith, and (vii) a method wherein components (a) and
(b) are first mixed and contacted with each other, then the solid
carrier, then component (c) and further again component (b) are
mixed and contacted therewith.
The fourth olefin polymerization catalyst (C-4) according to the
present invention is characterized in that a polymer having a
Z-average molecular weight of 6,000,000 or more by gel permeation
chromatography and having a die-swell ratio of 1.4 or more,
obtained by contacting ethylene, or ethylene and a C4 to C10
.alpha.-olefin, with a catalyst comprising a solid carrier, (A) a
solid transition metal catalyst component obtained by contacting
(a) a compound of a transition metal of the group 4 in the periodic
table, containing at least one ligand having a cyclopentadienyl
skeleton, (b) an organoaluminum oxy compound, (c) a multifunctional
organic halide represented by the general formula (I), and (d) an
organoaluminum compound, and (B) an organoaluminum compound,
wherein 0.01 to 1000 g of the polymer is pre-polymerized per g of
the solid transition metal catalyst component.
The solid transition metal catalyst component can be prepared by
mixing and contacting the components (a), (b), (c) and (d) and the
solid carrier with each other in an inert hydrocarbon. The order of
mixing these components is arbitrary, but for the same reason as
described above, it is desirable that the components (a) and (c)
are not directly mixed and contacted with each other.
The preferable contact order includes, for example: (i) a method
wherein component (b) is mixed and contacted with the solid
carrier, then component (a) is contacted therewith, and then
components (c) and (d), or a contacted mixture of components (c)
and (d), is contacted therewith, (ii) a method wherein component
(b) is mixed and contacted with the solid carrier, then component
(c) is contacted therewith, and then component (a) or (d) is
contacted therewith, (iii) a method wherein components (a) and (b)
are first mixed and contacted with each other, and then the solid
carrier and then components (c) and (d) or a contacted mixture of
components (c) and (d) are mixed and contacted therewith, and (iv)
a method wherein the solid carrier is contacted with a contacted
mixture of components (b) and (c), and then component (a) or (d) is
mixed and contacted therewith.
When the respective components are mixed in the process of
preparing the solid catalyst component of the present invention, in
mixing the respective components, the component (a) is used in an
amount of 10.sup.-6 to 5.times.10.sup.-4 mole, preferably
5.times.10.sup.-6 to 2.times.10.sup.-4 mole, per g of the solid
carrier, and the concentration of the component (a) is in the range
of 10.sup.-5 to 10.sup.-2 mole/L in the solvent, preferably
5.times.10.sup.-5 to 5.times.10.sup.-3 mole/L in the solvent. The
component (b) is used in an amount of 10 to 1000, preferably 50 to
500, in terms of the atomic ratio (Al/transition metal) of aluminum
(Al) derived from the component (b) to the transition metal derived
from the component (a). The component (c) is used in an amount of
0.01 to 5.0 moles, preferably 0.02 to 1.0 mole, more preferably
0.03 to 0.5 mole, per mole of aluminum derived from the component
(b). When the component (d) is used, the component (d) is used in
such an amount that the gram atomic ratio (Al-d/Al-b) of the
aluminum atom (Al-d) in the component (d) to the aluminum atom
(Al-b) in the component (b) becomes 0.01 to 2.0, preferably 0.02 to
1.0.
The mixing temperature in mixing the respective components is -50
to 150.degree. C., preferably -20 to 120.degree. C., and the
contacting time is 1 to 1000 minutes, preferably 5 to 600 minutes.
During mixing and contacting, the mixing temperature may be
changed.
In a preferable contacting mode in the process for preparing the
solid catalyst component in the present invention, there is a
method wherein components (b) and (c) are previously mixed and
contacted with each other in an inert hydrocarbon to prepare a
solution containing components (b) and (c) mixed and contacted
therein, and then the solution is mixed and contacted with the
other components. When the components (b) and (c) are to be mixed
and contacted with each other, the concentration of component (b)
is 0.01 to 5 moles/L in the solvent, preferably 0.1 to 3 moles/L in
the solvent. The amount of component (c) is desirably 0.01 to 5.0
moles, preferably 0.02 to 1.0 mole, more desirably 0.03 to 0.5
mole, per mole of aluminum derived from the component (b). The
mixing time in mixing and contacting the components (b) and (c) is
-90.degree. C. to 150.degree. C., preferably -80.degree. C. to
120.degree. C., and the contacting time is 1 to 1000 minutes,
preferably 5 to 600 minutes.
Specific examples of the inert hydrocarbon used in preparing the
solid catalyst component in the present invention include aliphatic
hydrocarbons such as propane, butane, pentane, hexane, heptane,
octane, decane, dodecane and kerosene; alicyclic hydrocarbons such
as cyclopentane, cyclohexane and methylcyclopentane; aromatic
hydrocarbons such as benzene, toluene and xylene; halogenated
hydrocarbons such as ethylene chloride, chlorobenzene and
dichloromethane, or mixtures thereof.
In the third solid catalyst component (C-3) according to the
present invention, it is preferable that per g of the solid
carrier, the transition metal atom derived from the component (a)
is carried in an amount of 10.sup.-4 to 5.times.10.sup.-2 gram
atom, preferably 5.0.times.10.sup.-4 to 2.times.10.sup.-2 gram
atom, the aluminum atom derived from the component (b) is carried
in an amount of 10.sup.-4 to 1.0 gram atom, preferably
5.times.10.sup.-3 to 5.times.10.sup.-1 gram atom, and the component
(c) is carried in an amount of 5.times.10.sup.-5 to
5.times.10.sup.-2 mole, desirably 10.sup.-5 to 10.sup.-2 mole.
In the fourth solid catalyst component (C-4) according to the
present invention, it is preferable that per g of the solid
carrier, the transition metal atom derived from the component (a)
is carried in an amount of 5.times.10.sup.-5 to 5.times.10.sup.-2
gram atom, preferably 10.sup.-5 to 10.sup.-2 gram atom, the
aluminum atom derived from the components (b) and (d) is carried in
an amount of 10.sup.-3 to 1.0 gram atom, preferably
5.times.10.sup.-3 to 5.times.10.sup.-1 gram atom, and the component
(c) is carried in an amount of 5.times.10.sup.-5 to
5.times.10.sup.-2 mole, desirably 10.sup.-5 to 10.sup.-2 mole.
The third and fourth olefin polymerization catalysts (C-3) and
(C-4) according to the present invention are produced by
pre-polymerizing ethylene and .alpha.-olefin in the presence of the
solid catalyst components, and the Z-average molecular weight of
the pre-polymer obtained by such pre-polymerization is 6,000,000 or
more as determined by gel permeation chromatography, and the
die-swell ratio thereof is 1.4 or more.
The .alpha.-olefin used in pre-polymerization includes propylene,
1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene,
1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and
1-eicosene. Among these, ethylene or a combination of ethylene and
the .alpha.-olefin used in polymerization is particularly
preferable. The polymerization system may be any of batch,
semi-continuous and continuous systems, and an arbitrary method can
be selected from slurry polymerization, gaseous-phase
polymerization and solution polymerization methods.
The polymerization solvent used in slurry polymerization or
solution polymerization includes, for example, aliphatic
hydrocarbons such as propane, butane, pentane, hexane, heptane,
octane, decane, dodecane and kerosene; alicyclic hydrocarbons such
as cyclopentane, cyclohexane and methylcyclohexane; aromatic
hydrocarbons such as benzene, toluene and xylene; halogenated
hydrocarbons such as ethylene chloride, chlorobenzene,
dichloromethane and chloroform. These solvents may be used alone or
as a mixture of two or more thereof. The olefin itself can also be
used as the solvent.
In the pre-polymerization, the component (a) is used in an amount
(in terms of transition metal) of 10.sup.-6 to 5.times.10.sup.-4
mole, preferably 5.times.10.sup.-6 to 2.times.10.sup.-4 mole, per g
of the solid carrier. The component (b) is used in an amount of 10
to 1000, preferably 50 to 500, in terms of the atomic ratio
(Al/transition metal) of aluminum (Al) in the component (b) to the
transition metal in the component (a). The component (c) is used in
an amount of 0.01 to 5.0 mole, preferably 0.02 to 1.0 mole, more
preferably 0.03 to 0.5 mole, per mole of the component (b). When
the component (d) is to be used, the component (d) is used in such
an amount that the gram atomic ratio (Al-d/Al-b) of the aluminum
atom (Al-d) in the component (d) to the aluminum atom (Al-b) in the
component (b) is 0.01 to 5.0, preferably 0.02 to 1.0.
The concentration in the pre-polymerization system using the
transition metal compound (a) or the solid catalyst component
formed from the respective components is usually 10.sup.-6 to
2.times.10.sup.-1 mole/L, desirably 5.times.10.sup.-5 to 10.sup.-1
mole/L, in terms of transition metal per of polymerization
volume.
The pre-polymerization temperature is -20 to 90.degree. C.,
preferably 0 to 80.degree. C., the pre-polymerization time is 0.5
to 100 hours, preferably 1 to 80 hours, and the pre-polymerization
pressure is normal pressure to 10 MPa, preferably normal pressure
to 5 MPa.
In the pre-polymerization, the same olefin as used in
polymerization described later is usually used, but preferably an
olefin based on ethylene is used.
In the pre-polymerized catalyst, an olefin may be introduced into
an olefin polymerization catalyst suspension prepared by using an
inert hydrocarbon solvent, or an olefin polymerization catalyst
formed in an inert hydrocarbon solvent may be separated from the
suspension and then suspended again in an inert hydrocarbon,
followed by introducing an olefin into the resulting
suspension.
By pre-polymerization, an olefin polymer (preliminary polymer) is
desirably formed in an amount of 0.01 to 1000 g, preferably 0.1 to
800 g, more preferably 0.2 to 500 g, per g of the solid
carrier.
The slurry concentration is preferably lower to increase the
molecular weight of the prepolymer obtained by pre-polymerization,
but in consideration of productivity, the concentration of the
solid catalyst component per L of the solvent is 0.5 to 500 g/ml,
preferably 1 to 400 g/ml. The Z-average molecular weight as one
property of the prepolymer obtained by pre-polymerization is
preferably in the range of 6,000,000 to 100,000,000, more
preferably 7,000,000 to 100,000,000. The die-swell ratio meaning
the presence of long branches, as another property of the
prepolymer, is preferably in the range of 1.4 to 5.0, more
preferably 1.7 to 3.0.
The number-average molecular weight (Mn), weight-average molecular
weight (Mw) and Z-average molecular weight (Mz) were calculated
from a molecular-weight distribution curve obtained from a Waters
model "Alliance GPC 2000" gel permeation chromatograph
(high-temperature size exclusion chromatograph). The operation
conditions are as follows:
<<Used apparatus and Conditions>>
Measurement apparatus: Gel permeation chromatograph Alliance GPC
2000 model (Waters) Analysis software: Chromatography data system
Empower (Waters) Columns: TSK gel GMH.sub.6-HT.times.2+TSK gel
GMH.sub.6-HTL.times.2 (inner diameter 7.5 mm.times.length30 cm,
Tosoh Corporation) Mobile phase: o-dichlorobenzene [=ODCB] (special
grade, Wako Pure Chemical Industries, Ltd.) Detector: Differential
refractometer (built-in meter in the apparatus) Column temperature:
140.degree. C. Flow rate: 1.0 mL/min. Injection volume: 500 .mu.L
Sampling interval: 1 second Sample concentration: 0.15% (w/v)
Molecular weight calibration: From monodisperse polystyrene (Tosoh
Corporation)/molecular weight 495.
A molecular weight of 20,600,000, molecular weight distribution,
and various average molecular weights were calculated as PE
equivalent molecular weight according to widely used calibration
procedures described in a literature [Z. Crubisic, P. Rempp, H.
Benoit, J. Polym. Sci., B5, 753 (1967)]
The die-swell ratio of the polymer obtained by pre-polymerization
was determined by the following method.
[Preparation of A Measurement Sample]
To prevent a scatter of physical properties, the resulting
pre-polymerized catalyst was subjected to melt kneading by the
following method. 0.1 wt % Irganox 1076 (Ciba Specialty Chemicals)
and 0.1 wt % Irgafos 168 (Ciba Specialty Chemicals) were added as
heat stabilizers to the resulting pre-polymerized catalyst which
was then melt-kneaded at a resin temperature of 180.degree. C. at a
revolution number of 50 rpm for 5 minutes in a Laboplast mill
manufactured by Toyo Seiki Seisaku-sho, Ltd. This melted
pre-polymerized catalyst was cooled under the conditions of a
cooling temperature of 20.degree. C., a cooling time of 5 minutes
and a press pressure of 100 kg/cm.sup.2 with a press molding
machine manufactured by Shinto Metal Industries, Ltd.
[Measurement of Die-swell Ratio (SR)]
The die-swell ratio (SR) was measured by a capillary rheometer
(Capillograph 1B (barrel diameter 10 mm.phi.)) manufactured by Toyo
Seiki Seisaku-sho, Ltd. The measurement sample, 10 g, was melted at
a temperature of 190.degree. C. for 6 minutes and then extruded at
an extrusion speed of 5.0 mm/min. through a capillary shown in
FIGS. 6 and 7. A strand extruded by about 30 mm from an outlet of
the capillary was sampled and cooled at room temperature for 1
minute. The diameter of the strand was measured at arbitrary five
points, and the average diameter was indicated as strand diameter.
A value obtained by dividing the strand diameter by the capillary
diameter (4.5 mm) was indicated as die-swell ratio (SR).
Then, the method of polymerizing an olefin according to the present
invention is described. In the present invention, olefin
polymerization is carried out in the presence of the olefin
polymerization catalyst described above. The polymerization can be
carried out in liquid phase polymerization such as suspension
polymerization or in gaseous phase polymerization. In the liquid
phase polymerization, the same inert hydrocarbon as used in
producing the olefin polymerization catalyst described above can be
used as the solvent, or the olefin itself can also be used as the
solvent.
When olefin polymerization is conducted by using the olefin
polymerization catalyst of the present invention, the above
catalyst is used in an amount of 10.sup.-6 to 2.times.10.sup.-2
mole/L (polymerization volume), desirably 5.times.10.sup.-5 to
10.sup.-2 mole/L (polymerization volume), in terms of the
concentration of the transition metal atom derived from the
component (a) in the polymerization system. If desired, an
organoaluminum oxy compound may be used. The amount of the
organoaluminum oxy compound used is desirably in the range of 0 to
500 moles per gram atom of the transition metal atom derived from
the component (a).
When the slurry polymerization is carried out, the polymerization
temperature of the olefin is desirably in the range of -50 to
100.degree. C., preferably 0 to 90.degree. C., and when the liquid
phase polymerization is carried out, the polymerization temperature
is desirably in the range of 0 to 250.degree. C., preferably 20 to
200.degree. C. When the gaseous phase polymerization is carried
out, the polymerization temperature is desirably in the range of 0
to 120.degree. C., desirably 20 to 100.degree. C. The
polymerization pressure is under the conditions of normal pressure
to 10 MPa, preferably normal pressure to 5 MPa, and the
polymerization reaction can also be carried out in any method of a
batch, semi-continuous or continuous system. The polymerization can
also be carried out in two or more stages different in reaction
conditions.
The molecular weight of the resulting olefin polymer can be
regulated by allowing hydrogen to be present in the polymerization
system or by changing the polymerization temperature. The olefin
polymerizable by the olefin polymerization catalyst of the present
invention includes ethylene and C4 to C10 .alpha.-olefins such as
1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and
1-decene; and C5 to C20 cyclic olefins such as cyclopentene,
cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene
and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronapht
halene. Further, styrene, vinyl cyclohexane and diene can be
used.
The bulk density of the resulting olefin polymer is 0.2 to 0.6
g/cc, more preferably 0.3 to 0.55 g/ml. The bulk density was
determined according to JIS K-6721.
(3) Use of the Ethylene-Based Polymer
A thermoplastic resin composition excellent in moldability and
mechanical strength is obtained by blending the ethylene-based
polymer according to the present invention with another
thermoplastic resin. The blending ratio of the ethylene-based
polymer of the present invention to another thermoplastic resin is
99.1/0.1 to 0.1/99.9.
As another thermoplastic resin, crystalline thermoplastic resin
such as polyolefin, polyamide, polyester and polyacetal, and
non-crystalline thermoplastic resin such as polystyrene,
acrylonitrile/butadiene/styrene copolymer (ABS), polycarbonate,
polyphenylene oxide and polyacrylate are used. Polyvinyl chloride
is also preferably used.
Specific examples of the polyolefin include an ethylene based
polymer, propylene based polymer, butene based polymer,
4-methyl-1-pentene based polymer, 3-methyl-1-butene based polymer,
hexene based polymer etc. Among these polymers, an ethylene based
polymer, propylene based polymer and 4-methyl-1-pentene based
polymer are preferable, and when an ethylene based polymer is used,
it may be either the ethylene based polymer according to the
present invention or a conventional ethylene based polymer, or
maybe an ethylene/polar group-containing vinyl copolymer, but the
conventional ethylene based polymer is more preferable.
Specific examples of the polyester include aromatic polyesters such
as polyethylene terephthalate, polyethylene naphthalate,
polybutylene terephthalate etc.; and polycaprolactone,
polyhydroxybutyrate etc.
Specific examples of the polyamide include aliphatic polyamides
such as nylon-6, nylon-66, nylon-10, nylon-12, nylon-46 etc. and
aromatic polyamides produced from aromatic dicarboxylic acid and
aliphatic diamine.
Specific examples of the polyacetal include polyformaldehyde
(polyoxymethylene), polyacetaldehyde, polypropione aldehyde,
polybutyl aldehyde etc. Among these, polyformaldehyde is
particularly preferable.
The polystyrene may be a homopolymer of styrene or a binary
copolymer of styrene and acrylonitrile, methyl methacrylate or
.alpha.-methyl styrene.
The ABS used is preferably ABS containing 20 to 35 mol %
constitutional unit derived from acrylonitrile, 20 to 30 mol %
constitutional unit derived from butadiene and 40 to 60 mol %
constitutional unit derived from styrene.
The polycarbonate includes polymers obtained from
bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane,
2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl) butane
etc. In particular, a polycarbonate obtained from
2,2-bis(4-hydroxyphenyl)propane is preferable.
As the polyphenyloxide, poly(2,6-dimethyl-1,4-phenylene oxide) is
preferably used.
As the polyacrylate, polymethyl methacrylate or polybutyl acrylate
is preferably used.
The thermoplastic resins described above may be used alone or as a
mixture of two or more thereof. The thermoplastic resin is
particularly preferably polyolefin, more preferably an
ethylene-based polymer.
In addition to the thermoplastic resin described above, additives
such as a weatherability stabilizer, a heat stabilizer, an
antistatic agent, a slip inhibitor, an anti-blocking agent, a haze
inhibitor, a lubricant, a pigment, a dye, a nucleating agent, a
plasticizer, an aging inhibitor, an HCl absorber and an antioxidant
may be incorporated into the ethylene-based polymer according to
the present invention if needed in such a range that the object of
the present invention is not hindered.
The ethylene-based polymer according to the present invention, and
a resin composition containing the ethylene-based polymer, can be
processed into a molded product, preferably a film, excellent in
moldability and mechanical strength.
The ethylene-based polymer of the present invention is processed by
general film molding, blow molding, injection molding and extrusion
molding. The film molding includes extrusion lamination molding,
T-die film molding, inflation molding (air cooling, water cooling,
multi-stage cooling, high-speed processing) etc. The resulting film
can be used as a single-layer film, but can be endowed with various
functions by conversion into a multilayer film. In this case,
co-extrusion in each of the above molding methods can be mentioned.
For lamination of hardly co-extruded paper and barrier film
(aluminum foil, vapor-deposited film, coating film or the like),
attaching lamination molding methods such as extrusion lamination
molding and dry lamination can be mentioned. Preparation of a
high-function product by forming it into a multilayer through blow
molding, injection molding, or extrusion molding in co-extrusion
molding, is also feasible in the same manner as film molding.
Molded products by processing the ethylene-based polymer of the
present invention, and a thermoplastic resin composition containing
the ethylene-based polymer, include films, blown transfusion bags,
blown bottles, tubes, pipes and ruptured pipes by extrusion
molding, injection moldings such as articles for daily use, fibers,
and large molded products by rotational molding.
Films obtained by processing the ethylene-based polymer of the
present invention, and a thermoplastic resin composition containing
the ethylene-based polymer, are suitable for water-wrapping bags,
liquid soap-wrapping bags, liquid paper containers, laminated cloth
rolls, liquid wrapping bags of special shape (standing pouch etc.),
specification bags, heavy bags, wrapping film, sugar bags, oil
bags, various films such as food-wrapping films, transfusion bags
and agricultural materials. Further, the film may be used as a
multilayer film by attaching it to a base material such as nylon,
polyester etc.
Hereinafter, the present invention is described in more detail by
reference to the Examples, but the present invention is not limited
to the Examples.
EXAMPLES
Hereinafter, the present invention is described in more detail by
reference to the Examples, but the present invention is not limited
to the Examples.
Preparation of Solid Components (S1) to (S3)
Preparation of Solid Component (S1)
30 g silica (SiO.sub.2) dried at 250.degree. C. for 10 hours in a
nitrogen stream was suspended in 460 mL toluene and then cooled to
0.degree. C. 140 mL solution of methyl alumoxane (component b: a
product of Mitsui Chemicals, Inc.) (1.52 mmol/mL in terms of Al
atom) in toluene was added dropwise to the suspension over 1 hour
during which the temperature in the system was kept at 0 to
2.degree. C. Subsequently, the mixture was reacted at 0.degree. C.
for 30 minutes, then heated to 95.degree. C. over 1.5 hours and
reacted at this temperature for 4 hours. Thereafter, the
temperature of the reaction mixture was decreased to 60.degree. C.,
and the supernatant was removed by decantation. The solid component
thus obtained was washed 3 times with toluene, and toluene was
added thereto to prepare slurry of the solid component (S1) in
toluene. A part of the resulting solid component (S1) was collected
to examine its concentration, indicating that the slurry
concentration was 0.124 g/mL and the Al concentration was 0.463
mmol/mL.
Preparation of Solid Component (S2)
13 g silica (SiO.sub.2) dried at 250.degree. C. for 10 hours in a
nitrogen stream was suspended in 100 mL toluene and then cooled to
0.degree. C. 52.6 mL solution of methyl alumoxane (component b: a
product of Albemarle) (1.75 mmol/mL in terms of Al atom) in toluene
was added dropwise to the suspension over 1 hour during which the
temperature in the system was kept at 0 to 2.degree. C.
Subsequently, the mixture was reacted at 0.degree. C. for 30
minutes, then heated to 95.degree. C. over 1.5 hours and reacted at
this temperature for 4 hours. Thereafter, the temperature of the
reaction mixture was decreased to 60.degree. C., and the
supernatant was removed by decantation. The solid component thus
obtained was washed 4 times with toluene, and toluene was added
thereto to prepare slurry of the solid component (S2) in toluene. A
part of the resulting solid component (S) was collected to examine
its concentration, indicating that the slurry concentration was
0.1216 g/mL and the Al concentration was 0.575 mmol/mL. A part of
the supernatant was collected to examine its concentration,
indicating that the Al concentration was not higher than 0.001
mmol/mL.
Preparation of Solid Component (S3)
The solid component (S3) was prepared in the same manner as for the
solid component (S2) except that it was twice that the resulting
solid component after the reaction of methyl alumoxane was washed
with toluene. A part of the resulting solid component (S3) was
collected to examine its concentration, indicating that the slurry
concentration was 0.1665 g/mL and the Al concentration was 0.697
mmol/mL. A part of the supernatant was collected to examine its
concentration, indicating that the Al concentration was 0.0042
mmol/mL.
Preparation of Solid Catalyst Components (X-1) to (X-4)
Preparation of Solid Catalyst Component (X-1)
50 mL toluene was introduced into a 200-mL glass flask flushed
previously with nitrogen, and then charged under stirring with the
slurry of the solid component (S1) in toluene (2.0 g in terms of
solids content) prepared above. Then, 33.9 mL solution of ethylene
bis(indenyl) zirconium dichloride (component a) (0.0011 mmol/mL in
terms of Zr atom) in toluene was added dropwise thereto, and the
mixture was reacted at room temperature for 2 hours. Thereafter,
the supernatant was removed by decantation, and the remaining
solids were washed 3 times with toluene and converted into 100 mL
toluene slurry. Then, 135.8 mg tetrafluorohydroquinone (component
c) was introduced thereinto at room temperature, and the mixture
was heated to 40.degree. C. and reacted for 30 minutes. Thereafter,
the supernatant was removed by decantation, and the remaining
solids were washed 3 times with toluene and converted into 50 mL
toluene slurry. 50 mL solution of removed methyl alumoxane
(component b) (0.15 mmol/mL in terms of Al atom) in toluene, from
which trimethyl aluminum had been distilled away, was added
dropwise thereto at room temperature over 15 minutes, and then the
mixture was heated to 40.degree. C. and reacted for 30 minutes.
Thereafter, the supernatant was removed by decantation, and the
remaining solids were washed 3 times with toluene and 3 times with
hexane, followed by adding 100 mL decane, to prepare slurry of the
solid catalyst component (X-1) in decane. A part of the resulting
slurry of the solid catalyst component (X-1) in decane was
collected to examine its concentration, indicating that the Zr
concentration was 0.0263 mg/mL, and the Al concentration was 3.61
mg/mL.
Preparation of Solid Catalyst Component (X-2)
50 mL toluene was introduced into a 200-mL glass flask flushed
previously with nitrogen, and then charged under stirring with
slurry of a solid component in toluene (2.0 g in terms of solids
content and 9.9 mmol in terms of Al atom), prepared in the same
manner (reaction temperature and reaction time) as for the solid
component (S1). Then, 32.6 mL solution of ethylene bis(indenyl)
zirconium dichloride (component a) (0.001525 mmol/mL in terms of Zr
atom) in toluene was added dropwise thereto, and the mixture was
reacted at room temperature for 2 hours. Thereafter, the
supernatant was removed by decantation, and the remaining solids
were washed 3 times with toluene and converted into 100 mL toluene
slurry. Then, 363.1 mg tetrafluorohydroquinone (component c) was
introduced thereinto at room temperature, and the mixture was
heated to 40.degree. C. and reacted for 30 minutes. Thereafter, the
supernatant was removed by decantation, and the remaining solids
were washed 3 times with toluene and converted into 50 mL toluene
slurry. 50 mL solution of methyl alumoxane (component b, a product
of Albemarle) (0.199 mmol/mL in terms of Al atom) in toluene was
added dropwise thereto over 10 minutes, and the mixture was heated
to 40.degree. C. and reacted for 30 minutes. Thereafter, the
supernatant was removed by decantation, and the remaining solids
were washed 3 times with toluene and 3 times with decane, followed
by adding 75 mL decane, to prepare slurry of the solid catalyst
component (X-2) in decane. A part of the resulting slurry of the
solid catalyst component (X-2) in decane was collected to examine
its concentration, indicating that the Zr concentration was 0.0258
mg/mL, and the Al concentration was 2.88 mg/mL.
Preparation of Solid Catalyst Component (X-3)
208 mL toluene was introduced into a 400-mL glass flask flushed
previously with nitrogen, and then charged under stirring with the
slurry of the solid component (S2) in toluene (8.0 g in terms of
solids content) prepared above. Then, 126 mL solution of ethylene
bis(indenyl) zirconium dichloride (component a) (0.0015mmol/mL in
terms of Zr atom) in toluene was added dropwise thereto, and the
mixture was reacted at room temperature for 2 hours. Thereafter,
the supernatant was removed by decantation, and the remaining
solids were washed once with toluene and converted into 250 mL
toluene slurry. Then, 150 mL solution of 1.377 g
tetrafluorohydroquinone (component c) in toluene was introduced
thereinto at room temperature, and the mixture was heated to
40.degree. C. and reacted for 30 minutes. Thereafter, the
supernatant was removed by decantation, and the remaining solids
were washed once with toluene and converted into 250 mL toluene
slurry. 150 mL solution of methyl alumoxane (component b, a product
of Albemarle) (0.253 mmol/mL in terms of Al atom) in toluene was
added dropwise thereto over 10 minutes, and the mixture was heated
to 40.degree. C. and reacted for 30 minutes. Thereafter, the
supernatant was removed by decantation, and the remaining solids
were washed 3 times with toluene and 3 times with decane, followed
by adding 150 mL decane, to prepare slurry of the solid catalyst
component (X-3) in decane. A part of the resulting slurry of the
solid catalyst component (X-3) in decane was collected to examine
its concentration, indicating that the Zr concentration was 0.0892
mg/mL, and the Al concentration was 11.2 mg/mL.
Preparation of Solid Catalyst Component (X-4)
100 mL toluene was introduced into a 400-mL glass flask flushed
previously with nitrogen, and then charged under stirring with the
slurry of the solid component (S3) in toluene (4.0 g in terms of
solids content) prepared above. Then, 55.7 mL solution of ethylene
bis(indenyl) zirconium dichloride (component a) (0.0015 mmol/mL in
terms of Zr atom) in toluene was added dropwise thereto, and the
mixture was reacted at room temperature for 2 hours. Thereafter,
the supernatant was removed by decantation, and the remaining
solids were washed once with toluene and converted into 100 mL
toluene slurry. Then, 100 mL solution of 608.1 mg
tetrafluorohydroquinone (component c) in toluene was introduced
thereinto at room temperature, and the mixture was heated to
40.degree. C. and reacted for 30 minutes. Thereafter, the
supernatant was removed by decantation, and the remaining solids
were washed once with toluene and converted into 100 mL toluene
slurry. 100 mL solution of methyl alumoxane (component b, a product
of Albemarle) (0.167 mmol/mL in terms of Al atom) in toluene was
added dropwise thereto over 10 minutes, and the mixture was heated
to 40.degree. C. and reacted for 30 minutes. Thereafter, the
supernatant was removed by decantation, and the remaining solids
were washed 3 times with toluene and 3 times with decane, followed
by adding 75 mL decane, to prepare slurry of the solid catalyst
component (X-4) in decane. A part of the resulting slurry of the
solid catalyst component (X-4) in decane was collected to examine
its concentration, indicating that the Zr concentration was 0.069
mg/mL, and the Al concentration was 9.23 mg/mL.
Preparation of Pre-polymerized Catalysts
Preparation of Pre-polymerized Catalyst (Q-1)
500 mL purified heptane was introduced into an SUS autoclave having
an internal volume of 1 liter purged sufficiently with nitrogen,
and the liquid phase and gaseous phase were saturated with ethylene
by blowing ethylene. The autoclave was charged in an ethylene
atmosphere at 20.degree. C. with 0.375 mmol triisobutyl aluminum
(component B) and the solid catalyst component (X-3) (0.0254 mmol
in terms of zirconium atom) in this order. Polymerization was
carried out at 20.degree. C. for 8 hours at an ethylene pressure of
0.78 MPaG, and then the autoclave was depressurized, and the
ethylene in the autoclave was replaced by nitrogen. The reaction
mixture was transferred into a 1-L container sufficiently purged
with nitrogen, and then washed 3 times. with decane, and decane was
added thereto to prepare slurry of the pre-polymerized catalyst
component (Q-1) in decane. A part of the resulting slurry of the
pre-polymerized catalyst component (Q-1) in decane was collected to
examine the slurry concentration and the amount of the
pre-polymerized catalyst, indicating that the slurry concentration
was 0.1693 g/mL, and the amount of the pre-polymerized catalyst per
g of the solid catalyst component was 31 g/g solid catalyst
component. When gel permeation chromatography (GPC) and die-swell
ratio (SR) of the polymer obtained by pre-polymerization were
measured, the Mw of the prepolymer was 75.4.times.10.sup.4, the Mz
was 735.6.times.10.sup.4, and the SR was 1.8.
Example 1
Polymerization (Two-stage Polymerization)
<Former stage> 500 mL purified heptane was introduced into an
SUS autoclave having an internal volume of 1 liter purged
sufficiently with nitrogen, and the liquid phase and gaseous phase
were saturated with ethylene by blowing ethylene. The autoclave was
charged in an ethylene atmosphere at 20.degree. C. with 0.375 mmol
triisobutyl aluminum (component B) and the solid catalyst component
(X-1) prepared above (0.004 mmol in terms of zirconium atom) in
this order. Polymerization was carried out at 20.degree. C. for 30
minutes at an ethylene pressure of 0.78 MPaG, and then the
autoclave was depressurized, and the ethylene in the autoclave was
replaced by nitrogen. <Latter stage> Then, the atmosphere in
the system was replaced by a hydrogen/ethylene mixed gas (hydrogen
concentration: 0.55 vol %), and then 10 mL 1-hexene was added
thereto, and the mixture was heated to 80.degree. C. and
polymerized for 20 minutes at an ethylene pressure of 0.78 MPaG.
The resulting polymer was vacuum-dried for 10 hours to give 35.6 g
ethylene/1-hexene copolymer.
To prepare a measurement sample, 0.1 wt % Irganox 1076 (Ciba
Specialty Chemicals) and 0.1 wt % Irgafos 168 (Ciba Specialty
Chemicals) were added as a heat stabilizer to the resulting
ethylene-based polymer which was then melt-kneaded at a resin
temperature of 180.degree. C. at a revolution number of 50 rpm for
5 minutes in a Laboplast mill manufactured by Toyo Seiki
Seisaku-sho, Ltd. This melted polymer was cooled under the
conditions of a cooling temperature of 20.degree. C., a cooling
time of 5 minutes and a cooling pressure of 100 kg/cm.sup.2 with a
press molding machine manufactured by Shinto Metal Industries, Ltd.
The physical properties of the sample were measured. The results
are shown in Tables 1 and 2.
Example 2
Polymerization (Two-stage Polymerization)
Polymerization was conducted in the same manner as in Example 1
except that the polymerization time of 20 minutes in the latter
stage was changed to 14 minutes. The resulting polymer was
vacuum-dried for 10 hours to give 23.3 g ethylene/1-hexene
copolymer.
Using the resulting ethylene-based polymer, a measurement sample
was prepared in the same manner as in Example 1. The physical
properties of the sample were measured. The results are shown in
Tables 1 and 2.
Example 3
Polymerization (Two-stage Polymerization)
Polymerization was conducted in the same manner as in Example 1
except that the polymerization time of 20 minutes in the latter
stage was changed to 27 minutes. The resulting polymer was
vacuum-dried for 10 hours to give 46.7 g ethylene/1-hexene
copolymer.
Using the resulting ethylene-based polymer, a measurement sample
was prepared in the same manner as in Example 1. The physical
properties of the sample were measured. The results are shown in
Tables 1 and 2.
Example 4
500 mL purified heptane was introduced into an SUS autoclave having
an internal volume of 1 liter purged sufficiently with nitrogen,
and the liquid phase and gaseous phase were saturated with ethylene
by blowing ethylene. Then, the atmosphere in the system was
replaced by a hydrogen/ethylene mixed gas (hydrogen concentration:
0.45 vol %), and then 60 mL 1-hexene, 0.375 mmol triisobutyl
aluminum (component B) and 1.5 g pre-polymerized catalyst component
(Q-1) were introduced thereinto in this order. The mixture was
heated to 70.degree. C. and polymerized for 90 minutes at a
pressure of 0.78 MPaG. The resulting polymer was vacuum-dried for
10 hours to give 61.4 g ethylene/1-hexene copolymer.
Using the resulting ethylene-based polymer, a measurement sample
was prepared in the same manner as in Example 1. The physical
properties of the sample were measured. The results are shown in
Tables 1 and 2.
Example 5
500 mL purified heptane was introduced into an SUS autoclave having
an internal volume of 1 liter purged sufficiently with nitrogen,
and the liquid phase and gaseous phase were saturated with ethylene
by blowing ethylene. Then, the atmosphere in the system was
replaced by a hydrogen/ethylene mixed gas (hydrogen concentration:
0.55 vol %), and then 7.5 mL 1-hexene, 0.375 mmol triisobutyl
aluminum (component B) and 1.44 g pre-polymerized catalyst
component (Q-1) were introduced thereinto in this order. The
mixture was heated to 90.degree. C. and polymerized for 90 minutes
at a pressure of 0.78 MPaG. The resulting polymer was vacuum-dried
for 10 hours to give 15.6 g ethylene/1-hexene copolymer.
Using the resulting ethylene-based polymer, a measurement sample
was prepared in the same manner as in Example 1. The physical
properties of the sample were measured. The results are shown in
Tables 1 and 2.
Example 6
500 mL purified heptane was introduced into an SUS autoclave having
an internal volume of 1 liter purged sufficiently with nitrogen,
and the liquid phase and gaseous phase were saturated with ethylene
by blowing ethylene. Then, the atmosphere in the system was
replaced by a hydrogen/ethylene mixed gas (hydrogen concentration:
0.83 vol %), and then 15 mL 1-hexene, 0.375 mmol triisobutyl
aluminum (component B) and 1.5 g pre-polymerized catalyst component
(Q-1) were introduced thereinto in this order. The mixture was
heated to 8.degree. C. and polymerized for 270 minutes at a
pressure of 0.78 MPaG. The resulting polymer was vacuum-dried for
10 hours to give 50.8 g ethylene/1-hexene copolymer.
Using the resulting ethylene-based polymer, a measurement sample
was prepared in the same manner as in Example 1. The physical
properties of the sample were measured. The results are shown in
Tables 1 and 2.
Example 7
Polymerization (Two-stage Polymerization)
<Former stage> 500 mL purified heptane was introduced into an
SUS autoclave having an internal volume of 1 liter purged
sufficiently with nitrogen, and the liquid phase and gaseous phase
were saturated with ethylene by blowing ethylene. The autoclave was
charged in an ethylene atmosphere at 20.degree. C. with 0.375 mmol
triisobutyl aluminum (component B) and the solid catalyst component
(X-2) prepared above (0.001 mmol in terms of zirconium atom) in
this order. Polymerization was carried out at 20.degree. C. for 6
hours at an ethylene pressure of 0.78 MPaG, and then the autoclave
was depressurized, and the ethylene in the autoclave was replaced
by nitrogen. <Latter stage> Then, the atmosphere in the
system was replaced by a hydrogen/ethylene mixed gas (hydrogen
concentration: 0.38 vol %), and then 30 mL 1-hexene was added
thereto, and the mixture was heated to 70.degree. C. and
polymerized for 160 minutes at a pressure of 0.78 MPaG. The
resulting polymer was vacuum-dried for 10 hours to give 44.8 g
ethylene/1-hexene copolymer.
Using the resulting ethylene-based polymer, a measurement sample
was prepared in the same manner as in Example 1. The physical
properties of the sample were measured. The results are shown in
Tables 1 and 2.
Example 8
500 mL purified heptane was introduced into an SUS autoclave having
an internal volume of 1 liter purged sufficiently with nitrogen,
and the liquid phase and gaseous phase were saturated with ethylene
by blowing ethylene. Then, the atmosphere in the system was
replaced by a hydrogen/ethylene mixed gas (hydrogen concentration:
0.54 vol %), and then 15 mL 1-hexene, 0.375 mmol triisobutyl
aluminum (component B) and 1.5 g pre-polymerized catalyst component
(Q-1) were introduced thereinto in this order. The mixture was
heated to 80.degree. C. and polymerized for 110 minutes at a
pressure of 0.78 MPaG. The resulting polymer was vacuum-dried for
10 hours to give 37.5 g ethylene/1-hexene copolymer.
Using the resulting ethylene-based polymer, a measurement sample
was prepared in the same manner as in Example 1. The physical
properties of the sample were measured. The results are shown in
Tables 1 and 2.
Example 9
Polymerization (Two-stage Polymerization)
<Former stage> 500 mL purified heptane was introduced into an
SUS autoclave having an internal volume of 1 liter purged
sufficiently with nitrogen, and the liquid phase and gaseous phase
were saturated with ethylene by blowing ethylene. The autoclave was
charged in an ethylene atmosphere at 20.degree. C. with 0.375 mmol
triisobutyl aluminum (component B) and the solid catalyst component
(X-4) prepared above (0.002 mmol in terms of zirconium atom) in
this order. Polymerization was carried out at 20.degree. C. for 120
minutes at an ethylene pressure of 0.78 MPaG, and then the
autoclave was depressurized, and the ethylene in the autoclave was
replaced by nitrogen. <Latter stage> Then, the atmosphere in
the system was replaced by a hydrogen/ethylene mixed gas (hydrogen
concentration: 0.83 vol %), and then 15 mL 1-hexene was added
thereto, and the mixture was heated to 80.degree. C. and
polymerized for 40 minutes at a pressure of 0.78 MPaG. The
resulting polymer was vacuum-dried for 10 hours to give 43.7 g
ethylene/1-hexene copolymer.
Using the resulting ethylene-based polymer, a measurement sample
was prepared in the same manner as in Example 1. The physical
properties of the sample were measured. The results are shown in
Tables 1 and 2.
Example 10
Polymerization (Two-stage Polymerization)
<Former stage> 500 mL purified heptane was introduced into an
SUS autoclave having an internal volume of 1 liter purged
sufficiently with nitrogen, and the liquid phase and gaseous phase
were saturated with ethylene by blowing ethylene. The autoclave was
charged in an ethylene atmosphere with 20 mL-1-hexene, 0.375 mmol
triisobutyl aluminum [component B] and the solid catalyst component
(X-2) prepared above (0.002 mmol in terms of zirconium atom) in
this order. The mixture was heated to 80.degree. C. and polymerized
for 15 minutes at an ethylene pressure of 0.78 MPaG, and then the
autoclave was depressurized, and the ethylene in the autoclave was
replaced by nitrogen. <Latter stage> Then, the atmosphere in
the system was replaced by a hydrogen/ethylene mixed gas (hydrogen
concentration: 1.25 vol %), and then 10 mL 1-hexene was added
thereto, and the mixture was heated to 80.degree. C. and
polymerized for 180 minutes at a pressure of 0.78 MPaG. The
resulting polymer was vacuum-dried for 10 hours to give 41.6 g
ethylene/1-hexene copolymer.
Using the resulting ethylene-based polymer, a measurement sample
was prepared in the same manner as in Example 1. The physical
properties of the sample were measured. The results are shown in
Tables 1 and 2.
Comparative Example 1
Preparation of Solid Component (S)
179 g silica (SiO.sub.2) dried at 250.degree. C. for 10 hours in a
nitrogen stream was suspended in 2.75 L toluene and then cooled to
0.degree. C. 810 mL solution of methyl alumoxane (component b)
(1.52 mmol/mL interms of Al atom) in toluene was added dropwise to
the suspension over 1 hour during which the temperature in the
system was kept at 0 to 2.degree. C. Subsequently, the mixture was
reacted at 0.degree. C. for 30 minutes, then heated to 95.degree.
C. over 1.5 hours and reacted at this temperature for 4 hours.
Thereafter, the temperature of the reaction mixture was decreased
to 60.degree. C., and the supernatant was removed by decantation.
The solid component thus obtained was washed 3 times with toluene,
and toluene was added thereto to prepare 1225 mL slurry of the
solid component (S) in toluene. A part of the resulting solid
component (S) was collected to examine its concentration,
indicating that the slurry concentration was 0.203 g/mL and the Al
concentration was 0.985 mmol/mL. A part of the solid component (S)
was dried and examined for its composition, indicating that 131 mg
Al atom was contained per g of the solid component.
Preparation of Solid Catalyst Component (X)
5.00 L solution of ethylene bis(indenyl) zirconium dichloride
(component a) (1.21 mmol/L in terms of Zr atom) in toluene was
added dropwise under stirring at 75.degree. C. over 30 minutes to
the toluene slurry of the solid component (S) prepared above, and
the mixture was heated to 80.degree. C. and reacted at this
temperature for 2 hours. Thereafter, the supernatant was removed,
and the remaining solids were washed twice with hexane, and hexane
was added thereto to prepare 3.32 L slurry of the solid catalyst
component (X) in hexane. A part of the resulting solid catalyst
component (X) was dried and examined for its composition,
indicating that 2.1 mg Zr atom was contained per g of the solid
catalyst component.
Preparation of Preliminarily Polymerized Catalyst (X')
The hexane slurry of the solid catalyst component (X) obtained
above was cooled to 10.degree. C., and then ethylene was fed
successively to the system at normal pressures. In this step, the
temperature of the system was kept at 10 to 15.degree. C.
Thereafter, 133 mL solution of triisobutyl aluminum (component B)
in decane (1.0 mmol/mL in terms of Al atom) and 16.6 mL 1-hexene
were added thereto to initiate preliminary polymerization. After 15
minutes, the temperature of the system was increased to 35.degree.
C., but thereafter, the system temperature was kept at 32 to
35.degree. C. 70 minutes after the preliminary polymerization was
initiated, 5.5 mL 1-hexene was added again thereto. Further, 160
minutes and 220 minutes thereafter, 5.5 mL 1-hexene was similarly
added thereto.
275 minutes after the preliminary polymerization was initiated, the
atmosphere in the system was replaced by nitrogen to terminate the
preliminary polymerization. Then, the supernatant was removed, and
the remaining solids were washed twice with hexane, to give a
preliminarily polymerized catalyst (X') wherein 3 g polymer was
preliminarily polymerized per g of the solid catalyst component
(X).
Polymerization
Using a continuous fluidized bed gaseous phase polymerizer,
ethylene and 1-hexane were copolymerized at a total pressure of 20
kg/cm.sup.2-G, at a polymerization temperature of 80.degree. C. and
a gas lineal speed of 0.8 m/sec. The preliminarily polymerized
catalyst (X') prepared above was dried and fed continuously at a
rate of 10 g/hr, while ethylene, 1-hexene, hydrogen and nitrogen
were continuously fed so that the gas composition was kept constant
during the polymerization (gas composition:
1-hexene/ethylene=1.1.times.10.sup.-2, ethylene concentration=62%)
The yield of the resulting ethylene/1-hexene copolymer was 6.1
kg/hr.
Using the resulting ethylene-based polymer, a measurement sample
was prepared in the same manner as in Example 1. The physical
properties of the sample were measured. The results are shown in
Tables 1 and 2.
Comparative Example 2
Product pellets of ethylene/1-hexene copolymer (trade name: EVOLUE
SP1520) produced by gaseous phase polymerization, commercially
available from Mitsui Chemicals, Inc. were used to prepare a
measurement sample to evaluate its physical properties. The results
are shown in Tables 1 and 2.
Comparative Example 3
Product pellets of ethylene/1-octene copolymer (trade name:
Affinity PF1140) produced by solution polymerization, commercially
available from Dow Chemical Company, were used to prepare a
measurement sample to evaluate its physical properties. The results
are shown in Tables 1 and 2.
In Comparative Examples 1, 2 and 3, LNR and MT/.eta.* were outside
of the requirements described in claims 1 and 2. Accordingly, the
neck-in of the products during molding is estimated to be higher
than that of the products in Examples 1 to 9.
Comparative Example 4
Product pellets of polyethylene (trade name: MIRASON M11) produced
by high-pressure radical polymerization, commercially available
from Mitsui Chemicals, Inc. were used to prepare a measurement
sample to evaluate its physical properties. The results are shown
in Tables 1 and 2.
In Comparative Example 4, the take-up speed at break (DS) is
outside of the requirements described in claim 1. Accordingly, the
product is estimated to inferior in high-speed film processability
to the products in Examples 1, 2, 4, 5 and 7. Further, the sum of
methyl branches and ethyl branches (A+B) is outside of the
requirements described in claim 1. Accordingly, the product is
estimated to be inferior in mechanical strength to the products in
Examples 1 to 9.
Comparative Example 5
Product pellets of ethylene/1-hexene copolymer (trade name: Marlex
HHM5502) commercially available from Phillips were used to prepare
a measurement sample to evaluate its physical properties. The
results are shown in Tables 1 and 2.
In Comparative Example S, LNR and MT/.eta.* are outside of the
requirements described in claims 1 and 2. Accordingly, the neck-in
of the product during molding is estimated to be higher than that
of the products in Examples 1 to 9. Further, the number of terminal
vinyl groups (V) per molecular chain is outside of the requirements
described in claim 3. Accordingly, the product is estimated to be
inferior in thermal stability during molding processing to the
products in Examples 1 to 9.
Comparative Example 6
Product pellets of ethylene/1-hexene copolymer (trade name:
Toughsen TUF-2060) commercially available from Nippon Unicar
Company Limited were used to prepare a measurement sample to
evaluate its physical properties. The results are shown in Tables 1
and 2.
Comparative Example 7
Product pellets of ethylene/1-hexene copolymer (trade name:
Toughsen TUF-2070) commercially available from Nippon Unicar
Company Limited were used to prepare a measurement sample to
evaluate its physical properties. The results are shown in Tables 1
and 2.
Comparative Example 8
Product pellets of ethylene/1-hexene copolymer (trade name:
Sumikasen-.alpha.GZ701) commercially available from Sumitomo
Chemical Co., Ltd. were used to prepare a measurement sample to
evaluate its physical properties. The results are shown in Tables 1
and 2.
In Comparative Examples 6 to 8, LNR and MT/.eta.* are outside of
the requirements described in claims 1 and 2. Accordingly, the
neck-in of these products during molding is estimated to be higher
than the products in Examples 1 to 9. Further, the relationship
between the melting-point maximum peak (Tm) and the density (d) is
outside of the requirements described in claim 3. Accordingly,
these products are estimated to be inferior in low-temperature
sealing properties to the products in Examples 1 to 9.
TABLE-US-00001 TABLE 1 Sum of Me branches and MFR Density .eta.*
MT/.eta.* Et branches DS Comonomer g/10 min. kg/m.sup.3 MT g P g/P
(A + B)/1000C LNR -- m/min *2 *3 Example 1 Hexene-1 6.71 945 6.4
1.85 .times. 10.sup.4 3.46 .times. 10.sup.-4 0.47 1.16 66 36 495
Example 2 Hexene-1 5.36 948 7.8 2.08 .times. 10.sup.4 3.75 .times.
10.sup.-4 0.11 1.16 50 32 435 Example 3 Hexene-1 6.77 945 6.5 1.88
.times. 10.sup.4 3.46 .times. 10.sup.-4 0.09 1.21 Example 4
Hexene-1 16.1 900 1.6 5.88 .times. 10.sup.3 2.72 .times. 10.sup.-4
*1 1.09 131 60 820 Example 5 Hexene-1 2.43 945 10.8 3.68 .times.
10.sup.4 2.93 .times. 10.sup.-4 0.29 1.17 38 20 275 Example 6
Hexene-1 30.7 941 2.8 3.75 .times. 10.sup.3 7.46 .times. 10.sup.-4
0.45 1.04 Example 7 Hexene-1 1.93 925 11 4.60 .times. 10.sup.4 2.40
.times. 10.sup.-4 0.36 1.06 39 18 241 Example 8 Hexene-1 7.70 934
3.8 1.34 .times. 10.sup.4 2.83 .times. 10.sup.-4 0.21 1.18 Example
9 Hexene-1 15.8 939 7.1 8.62 .times. 10.sup.3 8.24 .times.
10.sup.-4 0.64 0.94 Example 10 Hexene-1 6.29 931 9.1 2.14 .times.
10.sup.4 4.25 .times. 10.sup.-4 0.25 1.07 Comparative Hexene-1 1.99
919 3.9 5.94 .times. 10.sup.4 6.57 .times. 10.sup.-5 0.16 1.54
Example 1 Comparative Hexene-1 1.86 913 0.83 3.68 .times. 10.sup.4
2.25 .times. 10.sup.-5 *1 2.86 Example 2 Comparative Octene-1 1.70
899 2.0 5.85 .times. 10.sup.4 3.35 .times. 10.sup.-5 *1 2.10 225 16
224 Example 3 Comparative -- 7.06 918 3.8 1.49 .times. 10.sup.4
2.56 .times. 10.sup.-4 9.40 1.00 33 37 510 Example 4 Comparative
Hexene-1 0.32 958 12.0 1.44 .times. 10.sup.5 8.36 .times. 10.sup.-5
*1 1.59 Example 5 Comparative Hexene-1 2.47 924 0.85 3.45 .times.
10.sup.4 2.47 .times. 10.sup.-5 0.30 2.40 Example 6 Comparative
Hexene-1 3.02 939 0.75 2.85 .times. 10.sup.4 2.63 .times. 10.sup.-5
0.27 2.43 Example 7 Comparative Hexene-1 5.97 921 0.27 1.46 .times.
10.sup.4 1.85 .times. 10.sup.-5 0.90 2.49 Example 8 *1: Detection
lower limit (0.02/1000C) or less *2: Value of 12 .times.
MFR.sup.0.577 *3: Value of 165 .times. MFR.sup.0.577
TABLE-US-00002 TABLE 2 Number of terminal Number of vinyl groups
terminal vinyl GPC (v)/ groups (V)/ Tm Mn Mw Mz Mw/Mn Mz/Mw 1000C 1
molecular chain .degree. C. *4 *5 Example 1 9000 84000 2800000 9.49
33.4 0.19 0.12 120.0 97.7 127.7 Example 2 9000 110000 4100000 11.6
38.3 0.19 0.12 120.0 98.6 128.6 Example 3 8000 82000 4400000 10.2
54.8 0.16 0.09 120.0 97.7 127.7 Example 4 9500 52000 2000000 5.43
39.4 0.21 0.14 88.1 83.5 113.5 Example 5 13000 97000 4000000 7.36
41.7 0.12 0.11 124.0 97.7 127.7 Example 6 8600 91000 5200000 10.5
57.5 0.08 0.05 118.4 96.4 126.4 Example 7 8000 92000 3900000 11.5
42.4 0.13 0.07 117.7 91.4 121.4 Example 8 12000 80000 4300000 6.40
53.8 0.18 0.15 118.7 94.2 124.2 Example 9 11000 94000 5300000 8.89
56.9 0.14 0.11 119.0 95.8 125.8 Example 10 3600 82000 4300000 22.4
53.1 Comparative 20000 79000 280000 3.96 3.57 0.07 0.10 115.6 89.5
119.5 Example 1 Comparative 30000 73000 140000 2.41 1.96 0.08 0.17
113.6 87.6 117.6 Example 2 Comparative 29000 62000 120000 2.15 1.95
0.03 0.07 92.1 83.2 113.2 Example 3 Comparative 17000 150000 700000
8.55 4.78 0.04 0.05 104.1 89.2 119.2 Example 4 Comparative 18000
100000 1200000 5.87 11.2 0.76 0.95 131.7 101.8 131.8 Example 5
Comparative 20000 78000 310000 3.90 3.91 0.14 0.20 125.0 91.1 121.1
Example 6 Comparative 21000 74000 280000 3.54 3.74 0.19 0.29 126.7
95.8 125.8 Example 7 Comparative 14000 58000 170000 4.18 2.91 0.42
0.42 123.5 90.1 120.1 Example 8 *4: Value of 0.315 .times. d-200
*5: Value of 0.315 .times. d-170
INDUSTRIAL APPLICABILITY
The ethylene-based polymer of the present invention, and a
thermoplastic resin composition containing the ethylene-based
polymer, are used suitable in molded products, preferably films,
excellent in moldability and mechanical strength.
* * * * *